Process for making renewable surfactant intermediates and surfactants from fats and oils and products thereof

ABSTRACT

The present invention relates generally to methods for producing renewable detergent compounds. More specifically, the invention relates to methods for producing detergent intermediates, including bio-linear alkylbenzene (LAB), bio-alcohols, and long chain bio-paraffins, from natural oils.

FIELD OF THE INVENTION

The present invention relates generally to methods for producingrenewable detergent compounds. More specifically, the invention relatesto methods for producing detergent intermediates, including bio-linearalkylbenzene (LAB), bio-alcohols, and long chain bio-paraffins, fromnatural oils.

BACKGROUND OF THE INVENTION

While detergents made utilizing surfactant intermediates, such as alkylbenzenes, 2-alkyl alcohols (e.g., Isalchem®, Sasol), and primarilylinear alcohols (Neodol®, Shell), exist today, these surfactantintermediates are all made from conventional feedstocks, such aspetroleum-derived ethylene, kerosene, or other petrol materials. Due tothe growing environmental concerns over fossil fuel extraction andeconomic concerns over exhausting fossil fuel deposits, there is ademand for using an alternate feedstock for producing surfactants foruse in detergents.

The most significant challenge associated with providing renewablesurfactants, other than the conventional methyl ester sulphonatesproduced today from natural oils, is the capital cost of buildingentirely new production facilities. Furthermore, there is a need toprovide an efficient way to produce high purity bio-paraffins for use inproducing large volume, renewable detergent intermediates (e.g.,detergent alcohols, linear alkyl benzene (LAB)), either as a stand-alonedetergent intermediate production facility or integrated with anexisting detergent intermediate production facility. Productionapproaches that provide both renewable detergent alcohols and renewableLAB are especially desirable. Additionally, providing long chainrenewable feedstocks for the production of long chain renewable paraffinsulfonates, simultaneously with the production of renewable detergentalcohols and renewable LAB, may make the production of renewableparaffin sulfonates efficient and viable, as well.

Methods for processing natural fats, oils, and fatty acids intorenewable paraffins are known. However, these known methods are largelyfocused on biofuels, e.g., long chain renewable diesel. Much less isknown about methods for producing renewable paraffins for use in makingdetergent intermediates, where purity is more stringent. High purityparaffins are important for detergent intermediate manufacturing, e.g.,LAB production or production of detergent alcohols, where subsequentprocess steps are performed (e.g., dehydrogenation, alkylation,hydroformylation), involving various catatlysts. In contrast, biofuelsdo not require subsequent processing—biofuels are typically burned in acombustion engine. And, many of the desirable characteristics ofbiofuels are less desirable for detergent intermediates and detergentsurfactants that are used in cleaning products. For example, thepresence of impurities, such as branched compounds, unsaturatedcompounds, aromatic compounds, cyclic compounds, and compounds with somedegree of oxygen content is often desirable in a biofuel. For detergentintermediates, however, such impurities can form undesirable products,such as quaternary structures (which may have reduced biodegradability),under standard catalytic processes. And, many of the catalysts used inthe chemical processing of detergent intermediates do not tolerateimpurities, such as oxygenates, residual fatty acids, esters, andsubstantial branching.

A process for producing linear alkylbenzenes, paraffins, and olefinsfrom a feed source that includes a blend of natural oils, i.e., oilsthat are not extracted from the earth, and kerosene is known. However,the known process has limitations, namely it only allows for thesupplementing of a kerosene feed with natural oils, e.g., about 12% ofthe feed source is natural oils.

There is, therefore, a need to produce high purity linear paraffins fromrenewable materials. There is also a need to provide low-cost,integrated processes that make use of existing petrol-based productionfacilities. In particular, there is a need to produce linearalkylbenzenes, paraffins, and olefins from a feed source that includes ablend of natural oils and kerosene (petrol-based), where the feed sourcecontains a greater concentration of natural oil (e.g., greater thanabout 12% or greater than about 50% or greater than about 75%). There isalso a need to provide new stand-alone production facilities (outside ofexisting petrol-based production facilities) to produce renewablesurfactants. Renewable surfactants may be used to make sustainabledetergent formulations for consumer products, to meet the needs ofconsumers who desire sustainable products with good performance at anaffordable cost.

It has been found that by selecting certain process conditions, highpurity, renewable linear paraffins may be produced from natural oils,for use in making renewable detergent intermediates, such as LAB anddetergent alcohols. The process(es) of the invention may be integratedinto existing petrol-based production facilities or used in stand-aloneproduction facilities.

SUMMARY OF THE INVENTION

The present invention attempts to solve one more of the needs byproviding a method for producing an alkylbenzene and a detergent alcoholfrom a natural oil comprising:

-   -   a) providing a first feed stream comprising natural oil;    -   b) deoxygenating the first feed stream to form a stream        comprising paraffins;    -   c) removing volatile components and gases from the stream        comprising paraffins to form a purified paraffin stream;    -   d) fractionating the purified paraffin stream into three        fractions, where a first fraction comprises a lower boiling        range, a second fraction comprises a middle boiling range, and a        third fraction comprises a high boiling range;    -   e) dehydrogenating the first fraction to form a stream        comprising olefins;    -   f) alkylating the stream comprising olefins with a second feed        stream comprising benzene to form a stream comprising        alkylbenzenes;    -   g) dehydrogenating the second fraction to form a stream        comprising olefins and paraffins;    -   h) separating the olefins from the paraffins in the stream        comprising olefins and paraffins to form an olefin stream;    -   i) hydroformylating the olefin stream to form a stream        comprising detergent alcohols.

The present invention further relates to detergent compositionscomprising sulfonated linear alkylbenzene and/or sulfated detergentalcohol, produced according to the methods described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 schematically illustrates a commercial kerosene process forproducing alkylbenzenes and detergent alcohols

FIG. 2 schematically illustrates an integrated system for the productionof a blend of kerosene-based and renewable alkylbenzene as well as arenewable detergent alcohol.

FIG. 2a schematically illustrates the production of paraffin sulfonatefrom one of the cuts of paraffin produced in FIG. 2.

FIG. 3 schematically illustrates a known system for producing linearalkylbenzenes, paraffins, and olefins from a feed source that includes ablend of natural oils and kerosene.

FIG. 4 schematically illustrates a stand-alone system (outside of aconventional kerosene facility) to produce renewable linear paraffins,which are subsequently processed to produce renewable detergent alcoholand renewable alkylbenzene.

FIG. 5 schematically illustrates a system where a renewable LAB, madeusing the processes of the invention, is blended with a conventional,petrol-based LAB.

FIG. 6 schematically illustrates a system where a cut of bio-paraffin isblended with a cut of kerosene-based paraffin and subsequently processedto form a partially renewable 2-alkyl alkanol.

FIG. 7 schematically illustrates a stand-alone system (outside of aconventional kerosene facility) for producing renewable linearparaffins, which are subsequently processed to produce renewable 2-alkylalkanol and renewable alkylbenzene,

FIG. 8 schematically illustrates a stand-alone system (outside of aconventional kerosene facility) to produce renewable linear paraffins,which are subsequently processed to produce renewable 2-alkyl alkanol(with residual cuts of bio-paraffin going to other uses, such as fuel).

FIG. 9 schematically illustrates a stand-alone system (outside of aconventional kerosene facility) to produce renewable linear paraffins,which are subsequently processed to produce renewable alkylbenzene (withresidual cuts of bio-paraffin going to other uses).

DETAILED DESCRIPTION OF THE INVENTION

Features and benefits of the present invention will become apparent fromthe following description, which includes examples intended to give abroad representation of the invention. Various modifications will beapparent to those skilled in the art from this description and frompractice of the invention. The scope is not intended to be limited tothe particular forms disclosed and the invention covers allmodifications, equivalents, and alternatives falling within the spiritand scope of the invention as defined by the claims.

As used herein, articles such as “a” and “an” when used in a claim, areunderstood to mean one or more of what is claimed or described.

As used herein, the terms “include”, “includes” and “including” aremeant to be non-limiting.

As used herein, the term “LHSV” means Liquid Hourly Space Velocity.

As used herein, the term “GHSV” means Gasous Hourly Space Velocity.

As used herein, the term “LAS” refers to linear alkylbenzene sulfonate.

As used herein, the term “LAB” refers to linear alkylbenzene.

As used herein, the term “fatty alcohol” refers to a linear alcoholderived from a natural, renewable oil via reduction of the oil toalcohol (specifically, transesterification of triglycerides to givemethyl esters which in turn are hydrogenated to the alcohols). Fattyalcohols are essentially 100% linear.

As used herein, the term “detergent alcohol” is broader than the termfatty alcohol and encompasses fatty alcohols, which are essentially 100%linear, as well as synthetic alcohols, which may contain varying levelsof 2-alkyl branched content, depending on the process used to make thesynthetic alcohols, and linear content.

As used herein, the term “paraffin sulfonate” refers to a surfactantderived from sulfoxidation of paraffins.

As used herein, the term “renewable” (as in “renewable surfactantintermediate,” “renewable linear paraffin,” “renewable alkyl benzenesulfonate,” “renewable alcohol sulfate,” and “renewable paraffinsulfonate”) refers to materials (e.g., surfactant intermediates, linearparaffins, alkyl benzene sulfonates, alcohol sulfates, paraffinsulfonates) that are derived from a renewable feedstock and containrenewable carbon. A renewable feedstock is a feedstock that is derivedfrom a renewable resource, e.g., plants, and non-geologically derived. Amaterial may be partially renewable (less than 100% renewable carboncontent), 100% renewable (100% renewable carbon content), or somewherein between (e.g., 50% renewable carbon content). A renewable material,for example a renewable alkylbenzene, may be blended with anon-renewable, kerosene-based material, for example, a kerosene-basedalkylbenzene, to yield a partially renewable material, e.g., partiallyrenewable alkylbenzene.

As used herein, the term “geologically derived” means derived from, forexample, petrochemicals, natural gas, or coal. “Geologically derived”materials are materials that are mined from the ground (e.g., sulfur,sodium); “Geologically derived” materials cannot be easily replenishedor regrown (e.g., in contrast to plant- or algae-produced oils).

“Renewable carbon” may be assessed according to the “Assessment of theBiobased Content of Materials” method, which is disclosed herein.

The terms bio- and renewable (as in “bio-paraffin” and “renewableparaffin”) are used interchangeably. The term “renewable” is alsosynonymous with the term “sustainable,” “sustainably derived,” or “fromsustainable sources.”

The terms “kerosene-based” (as in “kerosene-based alkylbenzene”) andpetrol-based (as in “petrol-based alkylbenzene”) are usedinterchangeably to refer to a material (or the production thereof) thatis produced from kerosene or another petrochemical that is extractedfrom the earth. Kerosene-based and petrol-based materials arenon-renewable.

The term “substantially free of” or “substantially free from” as usedherein refers to either the complete absence of an ingredient or aminimal amount thereof merely as impurity or unintended byproduct ofanother ingredient. A composition that is “substantially free” of/from acomponent means that the composition comprises less than about 0.5%,0.25%, 0.1%, 0.05%, or 0.01%, or even 0%, by weight of the composition,of the component.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

Unless otherwise noted, all component or composition levels are inreference to the active portion of that component or composition, andare exclusive of impurities, for example, residual solvents orby-products, which may be present in commercially available sources ofsuch components or compositions.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

Method for Producing Alkylbenzene and/or Detergent Alcohol from aNatural Oil

The present invention relates to improved, highly efficient processesfor making renewable surfactant intermediates and renewable surfactants,which may be used in various cleaning products. More specifically, thepresent invention relates to methods and systems for producing a linearparaffin or olefin product from natural oils.

As used herein, the term “natural oils” means oils that are derived fromplant or algae matter (also referred to as renewable oils). Natural oilsare not based on kerosene or other fossil fuels. The term “oils” includefats, fatty acids, waste fats, oils, or mixtures thereof. Natural oilsinclude, but are not limited to, coconut oil, babassu oil, castor oil,algae byproduct, beef tallow oil, borage oil, camelina oil, Canola® oil,choice white grease, coffee oil, corn oil, Cuphea Viscosissima oil,evening primrose oil, fish oil, hemp oil, hepar oil, jatropha oil,Lesquerella Fendleri oil, linseed oil, Moringa Oleifera oil, mustardoil, neem oil, palm oil, perilla seed oil, poultry fat, rice bran oil,soybean oil, stillingia oil, sunflower oil, tung oil, yellow grease,cooking oil, and other vegetable, nut, or seed oils. The natural oilstypically include triglycerides, free fatty acids, or a combination oftriglycerides and free fatty acids, and other trace compounds.

Suitable natural oils may contain substantial levels of detergent-rangechain lengths, such as C10-18 range. The natural oil may be selectedfrom the group consisting of coconut oil, palm kernel oil, palm oil,kernel oil, rapeseed oil, canola oil, soybean oil, algae oil, cottonseedoil, Jatropha oil, babasu oil, fish oil, linseed oil, tall oil, tallow,poultry fat, camolina, cuphea, and mixtures thereof. The natural oil maybe selected from the group consisting of coconut oil, cuphea, palmkernel oil, palm oil, and poultry fat. The natural oil may be selectedfrom the group consisting of coconut oil, palm kernel oil, cuphea, andpalm oil. These oils contain the greatest concentration of triglyceridesand free fatty acids having chain lengths ranging from C10 to C18,particularly C10 to C16, which are especially useful in the detergentindustry. The natural oil feed stream may comprise triglycerides andfree fatty acids in the C10 to C18 chain length or in the C10 to C16chain length.

For reference, FIG. 1 illustrates the main processing steps of anexisting, conventional LAB and detergent alcohol facility that useskerosene extracted from the earth as a feed source. Crude oil is firstdistilled 1 to form kerosene and naphtha. The naptha is reformed 5 toform benzene. The kerosene is hydrotreated and sieved 2 to form C10-C13n-paraffins, C11-12 or C13-C14 n-paraffins, branched paraffins, andcyclic paraffins. The C10-C13 n-paraffins are dehydrogenated 3 to form aC10-C13 n-paraffin/olefin mixture. The C10-C13 n-paraffin/olefin mixtureis alkylated 4 with benzene to form linear alkylbenzene, and theremaining n-parrafin is distilled out. The C11/12 or C13-14 n-paraffinsare dehydrogenated 6 to form olefins, which are then separated out. Theolefins are hydroformylated 7 to form a mixture of detergent alcohol.The detergent alcohols produced may vary, depending on the selection ofthe hydroformylation catalyst in the hydroformylation unit 7. Any numberof detergent alcohols may be produced, including those containing somedegree of 2-alkyl branching. The detergent alcohols may containsubstantial amounts of linear detergent alcohols, depending on thechoice of the hydroformylation catalyst. These detergent alcohols aredifferent from the known renewable alcohols derived from methyl esters,such as CO-1214, CO-1270.

In a typical LAB and detergent alcohol co-production facility, as shownin FIG. 1, large amounts of kerosene are fed into the hydrotreatmentunit 2 for processing. Consequently, large amounts of material are fedinto the sieving unit 2 as well, since much of the kerosene feedstockcontains large amounts of cyclic, aromatics, branched paraffins, somelower levels of sulfur containing compounds, oxygenates, olefins, and,sometimes, nitrogen-containing compounds.

Hydrotreatment (also referred to as hydroprocessing) is a class ofcatalytic processes in a refinery scheme that comprises a set ofreactions. Hydrotreating involves non-destructive hydrogenation and isused to improve the quality of petroleum distillates without significantalteration of the boiling range. Hydrotreating generally employs mildtemperature and hydrogen pressures (in particular, as compared to theconditions of the process(es) of the invention), such that only the moreunstable compounds that might lead to the formation of gums, orinsoluble materials, are converted to more stable compounds.Hydrotreament is used to substantially remove sulfur, oxygenates,nitrogen, and aromatics prior to the sieving operation. Kerosenehydrotreatment units, kerosene hydrotreatment catalysts, processconditions, and configurations are well known in the petroleum art. Inregard to hydrotreating kerosene, kerosene contains very low levels ofoxygenates, as compared to natural oils. Therefore, the process ofhydrotreating kerosene, as known and described in the art, may producevery different results when applied to natural oils (as shown in theknown system of FIG. 3).

A typical kerosene composition contains between about 30% and about 50%linear paraffin. Thus, the hydrotreatment and sieving units are quitelarge versus other processes in the plant. Furthermore, to attain highpurity of the linear paraffin, e.g., greater than 99% purity, thesieving unit cannot remove all the linear paraffin cost effectivelywhile maintaining the very high purity required. Substantial loss oflinear paraffin to the reject stream—the branched, cyclic, and somelinear paraffin product from sieving unit—occurs and may only be usedfor jet fuel. Thus, expansion of any facility utilizing more kerosenefeed would require expansion of the hydrotreatment and the sievingunits.

In contrast, the deoxygenation of natural oils yields a much greaterlinear paraffin content—some 70-85% of the oil feedstock is renewableparaffin (versus only the sieved amount obtained from a keroseneunit—some 20-30% linear high purity paraffin). Thus, integrating theprocesses of the invention into an existing, conventional LAB and/or adetergent alcohol production plant, which utilizes kerosene feedstocks,may add substantially to the overall productivity of the subsequentprocessing steps in the kerosene-derived surfactant intermediates plant(e.g., by potentially greater than twice the kerosene production alonebased on the feed required to produce the same amount of surfactantintermediate).

The processes of the invention may be integrated into an existing,conventional LAB or a detergent alcohol production plant (or a combinedLAB and detergent alcohol production plant), which utilizes kerosenefeedstocks, thereby providing renewable linear paraffin intermediatesthat can be integrated into the plant to provide a source of renewablecarbon. Such an integrated process allows for the minimization ofadditional capital expense, provides a high purity renewable linearparaffin intermediates for integration into the plant, and mayefficiently increase the total production output of a facility withoutincreasing the kerosene-based units (e.g., kerosene hydrotreatment orabsorptive separation (sieving)). As illustrated in FIG. 2, theprocess(es) of the invention 8, 9, 10 may be readily integrated into anexisting, conventional LAB and/or a detergent alcohol production plantdownstream 13 from sieving unit 12, thereby maximizing the renewablecontent of the LAB and/or detergent alcohol (as well as, paraffinsulfonate, as shown in FIG. 2a ) produced in the facility withoutincreasing the kerosene-based units 11, 12, e.g., kero-hydrotreater.

In contrast, a known process for producing linear alkylbenzenes,paraffins, and olefins from a feed source that includes a blend ofnatural oils, i.e., oils that are not extracted from the earth, andkerosene is shown in FIG. 3. Importantly, in this known process, thekerosene (e.g., a heart cut, C10-C13, stream of kerosene) and thenatural oil are both processed in a conventional kerosene-based unit,such as a kero-hydrotreater 18. Hydrotreatment is followed by a step ofremoving volatile components and gases 19, sieving 20, and fractionating21, followed by either dehydrogenation and alkylation 24 ordehydrogenation 22, olefin separation 22, and non-selectivehydroformylation 23. Importantly, the kero-hydrotreater 18 receives boththe kerosene stream (e.g., a heart cut, C10-C13, stream of kerosene) andthe natural oil feed stream. The kero-hydrotreater 18 is employed totreat the heart cut stream of hydrocarbons to reduce the naturallyoccurring nitrogen and sulfur content in kerosene to acceptable levelsfor use in detergents. The kero-hydrotreater 18 is also configured todeoxygenate the natural oil feed to produce paraffins. The use of thekero-hydrotreater 18 to process both the kerosene and the natural oilplaces limitations on the process, namely it only allows for thesupplementing of a kerosene feed with natural oils, e.g., about 12% ofthe feed source is natural oils.

As illustrated in FIG. 2, a petroleum-derived linear paraffin stream maybe co-fed with a renewable linear paraffin stream, typically after asieving step or a dehydrogenation step (FIG. 2 shows after the sievingstep), to produce, for example, a partially renewable linear alkylbenzene. Depending on the volume production desired, it may also beadvantageous for production efficiency to blend a petroleum-derivedlinear paraffin stream with a renewable paraffin stream for theproduction of detergent alcohols 15, 16.

As shown in FIG. 2, the processes of the invention may employ separatenatural oil processing units 8, 9 that may be integrated into anexisting, conventional LAB and/or detergent alcohol production plant,such that the paraffin produced by these units or fractions thereof (theparaffin may be fractionated into selected cuts in a fractionation unit10) flows into the existing, conventional equipment downstream 13 fromthe sieving unit 12. This allows the renewable content of the feedsource to be maximized (e.g., greater than about 12% of the feed sourceis natural oils, or greater than about 50% of the feed source is naturaloils, or greater than about 75% of the feed source is natural oils)without increasing the kerosene-based unit(s) for hydrotreating 11,e.g., kero-hydrotreater, and sieving 12, thereby maximizing therenewable content of the LAB and/or detergent alcohol (as well as,paraffin sulfonate, as shown in FIG. 2a ) produced in the facility.

More specifically, in FIG. 2, the natural oil feed stream is deliveredto a deoxygenation unit 8, which also receives a hydrogen feed. In thedeoxygenation unit 8, the triglycerides and fatty acids in the feed aredeoxygenated and converted into linear paraffins. Structurally,triglycerides are formed from three, typically different, fatty acidmolecules that are bonded together with a glycerol bridge. The glycerolmolecule includes three hydroxyl groups (HO—), and each fatty acidmolecule has a carboxyl group (—COOH). In triglycerides, the hydroxylgroups of the glycerol join the carboxyl groups of the fatty acids toform ester bonds. During deoxygenation, the fatty acids are freed fromthe triglyceride structure and are converted into linear paraffins. Theglycerol is converted into propane, and the oxygen in the hydroxyl andcarboxyl groups is converted into either water or carbon dioxide. Thedeoxygenation reactions for fatty acids and triglycerides, respectively,are illustrated below:

During the deoxygenation reaction, the length of a product paraffinchain R^(n) will vary by a value of one, depending on the exact reactionpathway. For example, if carbon dioxide is formed, then the chain willhave one fewer carbons than the fatty acid source (R^(n)). If water isformed, then the chain will match the length of the R^(n) chain in thefatty acid source. Typically, due to the reaction kinetics, water andcarbon dioxide are formed in roughly equal amounts, such that equalamounts of C_(x) paraffins and C_(x-1) paraffins are formed. Thedeoxygenation process step, however, may be tuned (by selectingparticular catalysts and conditions) to produce a C8 to C18 linearparaffin product of suitable purity (as may be measured by gaschromatography (GC) analysis of the linear paraffin product). Forexample, for a feedstock that is C12, the deoxygenation process may betuned to alter the ratio of C11:C12 in the linear paraffin product,e.g., the deoxygenation process may be tuned to produce almost 100% C12linear paraffin product.

In FIG. 2, deoxygenation 8 is followed by a step of removing volatilecomponents and gases 9; a deoxygenated stream containing linearparaffins and volatile components and gases, such as water, carbondioxide, and propane, exits the deoxgenation unit 8 and is fed to aseparator 9. The separator 9 may be a multi-stage fractionation unit,distillation system, or a similar known apparatus. The separator 9removes the volatile components and gases from the deoxygenated stream.After the volatile components and gases are removed, a purifiedrenewable linear paraffin stream is formed. The purified linearbio-paraffin stream may have greater than 90% purity. The purifiedlinear bio-paraffin stream may have a branched paraffin content of lessthan about 5%, an olefin and cyclic content of less than about 3%, andan alcohol, ester, aldehyde, and fatty acid content of less than about2%.

The purified linear bio-paraffin stream may have greater than 95%purity. The purified linear bio-paraffin stream may have a branchedparaffin content of less than about 3%, an olefin and cyclic content ofless than about 1%, and an alcohol, ester, aldehyde and fatty acidcontent of less than about 1%. The purified linear bio-paraffin streammay have greater than 98% purity. The purified linear bio-paraffinstream may have a branched paraffin content of less than about 1.8%, anolefin and cyclic content of less than about 0.1%, and an alcohol,ester, aldehyde and fatty acid content of less than about 0.1%.

The process(es) described herein may be used to obtain a renewablelinear paraffin having a purity of from about 90% to about 100%, or fromabout 93% to about 100%, or from about 95% to about 100%, or from about98% to about 100%.

As shown in FIG. 2, the purified bio-paraffin stream may be fed into afractionation unit 10, which separates the purified bio-paraffins intovarious desirable chain length fractions or cuts. For example, as shownin FIG. 2, the purified bio-paraffin stream is fractionated into threecuts or fractions. Any number of fractions may be selected, depending onhow many fractions are desired. A first fraction of purifiedbio-paraffins may comprise lower boiling range bio-paraffins, a secondfraction may comprise middle boiling range bio-paraffins, and a thirdfraction may comprise high boiling range bio-paraffins. The firstfraction of purified bio-paraffins may comprise carbon chain lengths ofC10 to C14. Suitable fractions may include various combinations of chainlengths. For example, the first cut may be C10 to C12, the second cutmay be C13 to C14, and the third cut may be C15 to C18. Alternatively,the first cut may contain C10 to C13, the second cut may contain C14 toC16, and the third cut may contain C17 to C18. The cuts or fractions maybe selected to maximize the efficiency of the plant, by producingindividual cuts or various blends of cuts. Flexibility in terms offractionation also allows one to address the various needs of thedetergents manufacturer, including performance needs.

The first fraction of purified bio-paraffins may have carbon chainslengths having a lower limit of C_(M), where M is an integer from fourto thirty-one, and an upper limit of C_(N), where N is an integer fromfive to thirty-two. The second fraction of purified bio-paraffins mayhave carbon chains shorter than, longer than, or a combination ofshorter and longer than, the chains of the first fraction of purifiedbio-paraffins.

The purified bio-paraffin stream may be fractionated into three cuts. Asshown in FIG. 2, the first cut of purified bio-paraffin may be fed intoan alkylbenzene production unit(s) 13, 14, and the second cut may be fedinto an alcohol production unit(s) 15, 16. As shown in FIG. 2a , thethird cut may optionally be fed into a sulfoxidation unit 17 to formparaffin sulfonate.

More specifically, the first cut of purified bio-paraffin may be fedinto a dehydrogenation unit 13 and dehydrogenated to form a streamcomprising olefins and paraffins. Typically, dehydrogenation occursthrough known catalytic processes, such as the commercially popularPacol™ process. The stream comprising olefins and paraffins is thenalkylated 14 with a second feed stream comprising benzene to form astream comprising alkylbenzenes, as shown in FIG. 2. Any residualparaffin may be fed back into the dehydrogenation unit, as shown in FIG.2. The second cut of purified bio-paraffin may be fed into adehydrogenation unit and dehydrogenated to form a stream comprisingolefins and paraffins 15. The stream comprising olefins and paraffinsmay then fed into an olefin absorptive separation unit to separate theolefins from the paraffins 15. In FIG. 2, the dehydrogenation step andthe separation step are shown as part of a single unit 15. The olefinsmay then be subjected to hydroformylation 16 to form detergent alcohols.The steps of fractionation, sieving (for both linear paraffin and linearolefin), dehydrogenation, alkylation, and hydroformylation, as diagramedin the figures included herein, are well known in the art.

Thus, two renewable detergent intermediates and, optionally, a paraffinsulfonate may be produced in a single production plant. Alternatively,the first cut may be fed into an alcohol production unit to prepareshorter chain, renewable detergent alcohols. And, the third cut may befed into a detergent alcohol unit to produce longer chain renewabledetergent alcohols.

The renewable alkyl benzene and the renewable detergent alcohol mayfurther be sulfonated and sulfated by standard means to providerenewable surfactants for use in detergent formulations.

The invention also relates to mixtures of renewable alkylbenzenesulfonate and renewable alcohol sulfate for use in detergentformulations. Mixtures of renewable alkylbenzene sulfonate, renewablealcohol sulfate, and renewable paraffin sulfonate may also be obtained.Furthermore, the renewable surfactants produced by the method(s)disclosed herein may be combined with natural alcohol sulfates ornatural alcohol ethoxylated sulfates, such as those derived from thereduction of methyl esters to fatty alcohols. Such mixtures provide evengreater flexibility to the detergent formulator. Such mixtures alsoprovide improved performance for the consumer who desires a renewableformulation.

The invention also relates to a detergent composition that comprises arenewable surfactant content of at least about 50%, or at least about70%, or at least about 80%, or at least about 90% (meaning that at leastabout 50%, or at least about 70%, or at least about 80%, or at leastabout 90% of the total surfactant in the detergent composition isrenewable).

The processes of the invention may also be utilized in stand-alone unitsto produce renewable linear paraffins, outside of a conventionalkerosene facility; this may be economical for subsequent introductioninto a kerosene production facility or a facility that produces LAB frompurchased paraffin sources. FIG. 4 illustrates such a use. As shown inFIG. 4, the natural oil is deoxygenated 25, and deoxygenation 25 isfollowed by a step of removing volatile components and gases 26, to forma purified bio-paraffin. The purified bio-paraffin may be fractionated27 into any number of cuts, e.g., three cuts. Any one of the cuts orcombinations of cuts of purified bio-paraffin may be used to preparevarious renewable detergent alcohols. In FIG. 4, the second cut is shownfor illustration, but any combination of carbon cuts may be produced tomake various detergent alcohols, e.g., by blending the various cuts orcombinations of cuts into renewable detergent alcohols. In FIG. 4, thesecond cut is fed into an alcohol production unit(s) 30, 31 (todehydrogenate the second cut 30, separate out olefins 30, andhydroformylate the olefins 31) and the first cut is fed into analkylbenzene production unit(s) 28, 29 (to dehydrogenate 28 and alkylate29 the first cut).

Also, if renewable CO is used in the hydroformylation step 31 and/orrenewable benzene is used in the alkylation step 29, a 100% renewabledetergent alcohol mixture and/or a 100% renewable alkylbenzene may beproduced. Otherwise, a partially renewable detergent alcohol mixtureand/or a partially renewable alkylbenzene may be produced.

All in all, the processes described herein allow for maximum flexibilityin terms of incorporating renewable carbon content to produce renewablesurfactants. For example, FIG. 5 shows a system where a renewable LAB,made using the processes of the invention, is blended with aconventional, petrol-based LAB. As shown in FIG. 5, the natural oil isdeoxygenated 32, and deoxygenation 32 is followed by a step of removingvolatile components and gases 33, to form a purified bio-paraffin. Thepurified bio-paraffin may be fractionated 34 into any number of cuts,e.g., three cuts. In FIG. 5, the second cut is fed into an alcoholproduction unit(s) 41, 42 (to dehydrogenate the second cut 41, separateout olefins 41, and non-selectively hydroformylate the olefins 42). And,the first cut is fed into an alkylbenzene production unit(s) 35, 36 (todehydrogenate 35 and alkylate 36 the first cut) to produce renewablealkyl benzene, which may be blended with a petrol-based alkyl benzene.The petrol-based alkyl benzene is produced from kerosene, which ishydrotreated 37, sieved 38, dehydrogenated 39, and alkylated 40.

Also, FIG. 6, for example, shows a system where a second cut ofbio-paraffin (which is made using the processes of the invention)comprising, e.g., middle boiling range bio-paraffins, is blended with along-chain cut, e.g., C13-C15, of kerosene-based paraffin, andsubsequently processed to form a partially renewable (blended) 2-alkylalkanol. As shown in FIG. 6, the natural oil is deoxygenated 43, anddeoxygenation 43 is followed by a step of removing volatile componentsand gases 44, to form a purified bio-paraffin. The purified bio-paraffinmay be fractionated 45 into any number of cuts, e.g., three cuts. InFIG. 6, the second cut of purified bio-paraffin is blended with apetrol-based paraffin, e.g., C13-C15 paraffin, and the blend is fed intoan alcohol production unit(s) 50, 51 (to dehydrogenate the blend 50,separate out olefins 50, and non-selectively hydroformylate the olefins51). A different cut of petrol-based paraffin, e.g., C10-C13, is fedinto an alkylbenzene production unit(s) 49 (to dehydrogenate andalkylate the cut) to produce petrol-based alkyl benzene. Thepetrol-based paraffin is produced from kerosene, which is hydrotreated46, sieved 47, and fractionated 48.

Also, FIG. 8, for example, shows a system where a renewable 2-alkylalkanol mixture is formed. As shown in FIG. 8, the natural oil isdeoxygenated 59, and deoxygenation 59 is followed by a step of removingvolatile components and gases 60, to form a purified bio-paraffin. Thepurified bio-paraffin may be fractionated 61 into any number of cuts,e.g., three cuts. In FIG. 8, the second cut of purified bio-paraffin isfed into an alcohol production unit(s) 62, 63 (to dehydrogenate thesecond cut 62, separate out olefins 62, and non-selectivelyhydroformylate the olefins 63). The remaining cuts of purifiedbio-paraffin are employed for other uses.

Also, FIG. 9, for example, shows a system where a renewable alkylbenzeneis formed. As shown in FIG. 9, the natural oil is deoxygenated 64, anddeoxygenation 64 is followed by a step of removing volatile componentsand gases 65, to form a purified bio-paraffin. The purified bio-paraffinmay be fractionated 66 into any number of cuts, e.g., three cuts. InFIG. 9, the first cut of purified bio-paraffin is fed into analkylbenzene production unit(s) 67, 68 (to dehydrogenate 67 and alkylate68 the first cut) to produce a renewable alkyl benzene. The remainingcuts of purified bio-paraffin are employed for other uses.

Deoxygenation

It has been found that the deoxygenating step of the processes describedherein may be an important step in order to prepare the partially or100% renewable detergent alcohol mixture and/or the renewablealkylbenzene of the invention. In typical processing of natural oils,e.g., for biofuels, minor impurities, such as oxygenates, aromatics,cyclic and branched materials, are actually preferred for fuel mixtures.However, this is not the case in preparing surfactant intermediates foruse in consumer goods, such as laundry detergents and dish products. Ithas been discovered that by selecting certain catalysts, process design,and reaction conditions, such as hydrogen flow rate, hydrogen pressure,temperature, and liquid flow rates, high purity bio-paraffin, suitablefor detergent intermediate processing, may be produced. Certaindeoxygenation conditions may be particularly advantageous for producinga high purity, renewable linear paraffin stream from natural oils.

The method of deoxygenating a natural oil stream may comprise thestep(s) of reacting the natural oil stream in the presence of a Ni/Mocatalyst or a Co/Mo catalyst, at a temperature from about 340° C. toabout 410° C., at a hydrogen pressure from about 500 psi to about 2000psi, or from about 500 psi to about 1500 psi, at a GHSV from about 800to about 2000, and at a LHSV of about 0.25 to about 6, or about 0.25 to4.0, or about 0.5 to about 2.5.

The method of deoxygenating a natural oil stream may comprise thestep(s) of reacting the natural oil stream in the presence of a Ni/Mosulfurized catalyst or a Co/Mo sulfurized catalyst, at a temperaturefrom about 280° C. to about 360° C., at a hydrogen pressure from about500 psi to about 1500 psi, at a GHSV of about 800 to about 2000, and ata LHSV of about 0.25 to about 4.0, or 0.5 to about 2.5. The use of asulferized catalyst versus a non-sulferized catalyst may affect theratio of chain lengths in the paraffin product. Instead of using apresulfurized catalyst, the method of deoxygenating may include the useof dimethyldisulfide (DMDS) at low levels, e.g., about 0.1% to about 2%DMDS. The use of presulfurized or sulfurized catalysts may require SO₂removal after deoxygenation. Suitable commercial presulfurizeddeoxygenation catalysts include Criterion 534 ® SH (PS-CoMo) andAlbemarle KF-841 ® (PS-NiMo). Suitable commercial deoxygenationcatalysts are also available from UOP, Johnson Matthey, IFP, Clariant,and Criterion.

The method of deoxygenating a natural oil stream may comprise thestep(s) of reacting the natural oil stream in the presence of a Pd onalumina catalyst, at a temperature from about 370° C. to about 420° C.,at a hydrogen pressure from about 200 psi to about 1000 psi, at a GHSVof about 800 to about 2000, and at a LHSV of about 0.25 to about 4.0, orabout 0.5 to about 2.5. As discussed above, one may tune the processwithin the disclosed ranges of conditions to achieve an even greaterpurity, for example 95% purity or greater than 98% purity renewablelinear paraffins. Suitable catalysts are available from Johnson Mattheyor other suppliers of palladium catalysts. A suitable catalyst is 1-5%Pd on alumina or 1-5% Pd on carbon.

The deoxygenation conditions described above for the specific types ofcatalysts, e.g., Ni/Mo and Co/Mo catalysts, have been found to producehigh purity renewable linear paraffins, e.g., a purity of greater thanabout 90%. Typically, if the temperature is too high, then branchedparaffins are produced and cracking of the paraffin by the catalyst mayalso occur. If the pressure is too low, then olefins, fatty acids, andfatty alcohols may be formed; these olefins, fatty acids, and fattyalcohols are contaminants for subsequent processing steps. The selectionof GHSV and LHSV rates has also been found to contribute to theproduction of high purity renewable linear paraffins. In general, byselecting all five conditions—the catalyst, temperature, hydrogenpressure, GHSV, and LHSV—one can produce the high purity renewablelinear paraffins of the invention. Furthermore, one may tune thedeoxygenation process(es) described herein within the disclosed rangesof conditions to obtain a renewable linear paraffin having an evengreater purity, for example, greater than about 95% purity or greaterthan about 98% purity. Additional suitable commercial deoxygenationcatalysts for use in the invention include Haldor Topsoe TK-527®(Ni/Mo), Albemarle KF-848 ® (Ni/Mo), Haldor Topsoe TK-574 ® (Co/Mo).Suitable commercial deoxygenation catalysts are also available from UOP,Johnson Matthey, IFP, Clariant, and Criterion.

Any of the methods of deoxygenating described herein may be used in anyof the various systems described herein (e.g., FIGS. 2-10) to preparethe renewable detergent alcohols and/or renewable alkylbenzenes (and/orrenewable paraffin sulfonates) of the invention. A continuous flowreactor with the ability to have counter-current hydrogen gas flow maybe used for any of the methods of deoxygenating described herein.

Dehydrogenation and Hydroformylation

Any number of known catalysts may be used for dehydrogenation andhydroformylation. Furthermore, it is also know to produce high purityolefins via separation on various adsorbents, e.g., available from UOP.Any type of hydroformylation may be used to prepare the renewabledetergent alcohols of the invention, such as selective or non-selectivehydroformylation. Suitable selective catalysts may be obtained fromShell and suitable non-selective catalysts may be obtained from JohnsonMatthey, which supplies catalysts based on rhodium or cobalt. A suitablecatalyst is of the non-selective type and provides a substantial degreeof 2-alkyl alkanol formation, for example, greater than 25% 2-alkylalkanol, or greater than 50%, or greater than 90%.

A renewable detergent alcohol containing 100% renewable carbon may beproduced, for example, if a renewable source of carbon monoxide is usedin the preparation of such a detergent alcohol (e.g., the syngas usedmay be from biomass of any type). A 100%-renewable linear alkyl benzenemay be produced. In order to prepare a renewable linear alkyl benzenehaving 100% renewable carbon content, the alkylation unit may utilize arenewable source of benzene (e.g., from Virent). As shown in FIG. 7, anatural oil is deoxygenated 52, and deoxygenation 52 is followed by astep of removing volatile components and gases 53, to form a purifiedbio-paraffin. The purified bio-paraffin may be fractionated 54 into anynumber of cuts, e.g., three cuts. In FIG. 7, a first cut is fed into analkylbenzene production unit(s) 55, 56 (to dehydrogenate 55 and alkylate56). The alkylation step 56 may employ a renewable source of benzene toyield a 100% renewable alkylbenzene. In FIG. 7, a second cut is fed intoan alcohol production unit(s) 57, 58 (to dehydrogenate the second cut57, separate out olefins 57, and hydroformylate the olefins 58). Thehydroformylation step 58 may employ a renewable source of carbonmonoxide to yield a 100% renewable 2-alkyl alkanol mixture.

Detergent Compositions

The detergent compositions described herein may comprise a surfactant inan amount sufficient to provide desired cleaning properties. Thedetergent compositions may comprise from about 1% to about 75%, byweight of the composition, of a surfactant. The detergent compositionsmay comprise from about 2% to about 35%, by weight of the composition,of a surfactant. The detergent compositions may comprise from about 5%to about 10%, by weight of the composition, of a surfactant.

The detergent compositions may comprise a renewable surfactant contentof at least about 50%, or at least about 70%, or at least about 80%, orat least about 90% (meaning that at least about 50%, or at least about70%, or at least about 80%, or at least about 90% of the totalsurfactant in the detergent composition is renewable).

In particular, the detergent compositions may comprise a renewablesurfactant produced according to the methods described herein. Thedetergent compositions may comprise a renewable sulfonated linearalkylbenzene, a renewable sulfated detergent alcohol, and/or a renewableparaffin sulfonate produced according to the method(s) described herein.The detergent compositions may comprise a renewable surfactant producedby the method(s) disclosed herein in combination with natural alcoholsulfates and/or natural alcohol ethoxylated sulfates, such as thosederived from the reduction of methyl esters to fatty alcohols.

The detergent compositions may comprise a renewable surfactant producedby the method(s) disclosed herein in combination with a non-renewablesurfactant. The non-renewable surfactant may be selected from the groupconsisting of anionic surfactants, nonionic surfactants, cationicsurfactants, zwitterionic surfactants, amphoteric surfactants,ampholytic surfactants, and mixtures thereof.

Non-Renewable Anionic Surfactants

Non-limiting examples of suitable non-renewable anionic surfactantsinclude any conventional anionic surfactant. This may include a sulfatedetersive surfactant, for e.g., alkoxylated and/or non-alkoxylated alkylsulfate materials, and/or sulfonic detersive surfactants, e.g., alkylbenzene sulfonates. The non-renewable anionic surfactant may be amid-chain branched detersive surfactant, e.g., a mid-chain branchedanionic detersive surfactant, such as a mid-chain branched alkylsulphate and/or a mid-chain branched alkyl benzene sulphonate. Othernon-renewable anionic surfactants useful herein are the water-solublesalts of: paraffin sulfonates and secondary alkane sulfonates containingfrom about 8 to about 24 (and in some examples about 12 to 18) carbonatoms; alkyl glyceryl ether sulfonates, especially those ethers of C₈₋₁₈alcohols (e.g., those derived from tallow and coconut oil). Mixtures ofany of the above-described non-renewable anionic surfactants are alsouseful. Additional suitable non-renewable anionic surfactants includemethyl ester sulfonates and alkyl ether carboxylates.

Non-Renewable Nonionic Surfactants

The surfactant may comprise one or more non-renewable nonionicsurfactants. The detergent composition may comprise from about 0.1% toabout 40% by weight of the composition of a non-renewable nonionicsurfactant. The detergent composition may comprise from about 0.3% toabout 10% by weight of the composition of a non-renewable nonionicsurfactant.

Suitable non-renewable nonionic surfactants useful herein can compriseany conventional nonionic surfactant. These can include, for e.g.,alkoxylated nonionic surfactant and amine oxide surfactants. In someexamples, the detergent compositions may contain an ethoxylated nonionicsurfactant. Other non-limiting examples of nonionic surfactants usefulherein include: C₈-C₁₈ alkyl ethoxylates, such as, NEODOL® nonionicsurfactants from Shell; C₆-C₁₂ alkyl phenol alkoxylates; C₁₂-C₁₈ alcoholand C₆-C₁₂ alkyl phenol condensates with ethylene oxide/propylene oxideblock polymers such as Pluronic® from BASF; C₁₄-C₂₂ mid-chain branchedalcohols, BA; C₁₄-C₂₂ mid-chain branched alkyl alkoxylates, BAE_(x),wherein x is from 1 to 30; alkylpolysaccharides; specificallyalkylpolyglycosides; polyhydroxy fatty acid amides; and ether cappedpoly(oxyalkylated) alcohol surfactants. Suitable nonionic surfactantsalso include those sold under the tradename Lutensol® from BASF.

Non-Renewable Cationic Surfactants

The surfactant may comprise one or more non-renewable cationicsurfactants. The detergent compositions may comprise from about 0.1% toabout 10%, or about 0.1% to about 7%, or about 0.3% to about 5% byweight of the composition, of a surfactant selected from one or morenon-renewable cationic surfactants. The detergent compositions of theinvention may be substantially free of non-renewable cationicsurfactants.

Non-Renewable Zwitterionic Surfactants

Examples of non-renewable zwitterionic surfactants include: derivativesof secondary and tertiary amines, derivatives of heterocyclic secondaryand tertiary amines, or derivatives of quaternary ammonium, quaternaryphosphonium or tertiary sulfonium compounds. Suitable examples ofnon-renewable zwitterionic surfactants include betaines, including alkyldimethyl betaine and cocodimethyl amidopropyl betaine, C₈ to C₁₈ (forexample from C₁₂ to C₁₈) amine oxides, and sulfo and hydroxy betaines,such as N-alkyl-N,N-dimethylammino-1-propane sulfonate where the alkylgroup can be C₈ to C₁₈.

Non-Renewable Amphoteric Surfactants

Examples of non-renewable amphoteric surfactants include aliphaticderivatives of secondary or tertiary amines, or aliphatic derivatives ofheterocyclic secondary and tertiary amines in which the aliphaticradical may be straight or branched-chain and where one of the aliphaticsubstituents contains at least about 8 carbon atoms, or from about 8 toabout 18 carbon atoms, and at least one of the aliphatic substituentscontains an anionic water-solubilizing group, e.g. carboxy, sulfonate,sulfate. Examples of compounds falling within this definition are sodium3-(dodecylamino)propionate, sodium 3-(dodecylamino) propane-1-sulfonate,sodium 2-(dodecylamino)ethyl sulfate, sodium 2-(dimethylamino)octadecanoate, disodium 3-(N-carboxymethyldodecylamino)propane1-sulfonate, disodium octadecyl-imminodiacetate, sodium1-carboxymethyl-2-undecylimidazole, and sodiumN,N-bis(2-hydroxyethyl)-2-sulfato-3-dodecoxypropylamine. Suitableamphoteric surfactants also include sarcosinates, glycinates,taurinates, and mixtures thereof.

Combinations of Surfactants

The detergent compositions may comprise a renewable anionic surfactantand a renewable or non-renewable nonionic surfactant, e.g., C₁₂-C₁₈alkyl ethoxylate. The detergent compositions may comprise a renewablealkyl benzene sulfonates (LAS) and another, optionally renewable,anionic surfactant, e.g., C₁₀-C₁₈ alkyl alkoxy sulfates (AE_(x)S), wherex is from 1-30, where the renewable surfactants are produced accordingto the methods described herein. The detergent compositions may comprisea renewable anionic surfactant and a cationic surfactant, for example,dimethyl hydroxyethyl lauryl ammonium chloride. The detergentcompositions may comprise a renewable anionic surfactant and azwitterionic surfactant, for example, C12-C14 dimethyl amine oxide.

Adjunct Cleaning Additives

The detergent compositions of the invention may also contain adjunctcleaning additives. Suitable adjunct cleaning additives includebuilders, structurants or thickeners, clay soilremoval/anti-redeposition agents, polymeric soil release agents,polymeric dispersing agents, polymeric grease cleaning agents, enzymes,enzyme stabilizing systems, bleaching compounds, bleaching agents,bleach activators, bleach catalysts, brighteners, dyes, hueing agents,dye transfer inhibiting agents, chelating agents, suds supressors,softeners, and perfumes.

Enzymes

The detergent compositions described herein may comprise one or moreenzymes which provide cleaning performance and/or fabric care benefits.Examples of suitable enzymes include, but are not limited to,hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases,phospholipases, esterases, cutinases, pectinases, mannanases, pectatelyases, keratinases, reductases, oxidases, phenoloxidases,lipoxygenases, ligninases, pullulanases, tannases, pentosanases,malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase,laccase, and amylases, or mixtures thereof. A typical combination is anenzyme cocktail that may comprise, for example, a protease and lipase inconjunction with amylase. When present in a detergent composition, theaforementioned additional enzymes may be present at levels from about0.00001% to about 2%, from about 0.0001% to about 1% or even from about0.001% to about 0.5% enzyme protein by weight of the detergentcomposition.

In one aspect preferred enzymes would include a protease. Suitableproteases include metalloproteases and serine proteases, includingneutral or alkaline microbial serine proteases, such as subtilisins (EC3.4.21.62). Suitable proteases include those of animal, vegetable ormicrobial origin. In one aspect, such suitable protease may be ofmicrobial origin. The suitable proteases include chemically orgenetically modified mutants of the aforementioned suitable proteases.In one aspect, the suitable protease may be a serine protease, such asan alkaline microbial protease or/and a trypsin-type protease. Examplesof suitable neutral or alkaline proteases include:

(a) subtilisins (EC 3.4.21.62), including those derived from Bacillus,such as Bacillus lentus, B. alkalophilus, B. subtilis, B.amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii described inU.S. Pat. No. 6,312,936 B1, U.S. Pat. No. 5,679,630, U.S. Pat. No.4,760,025, U.S. Pat. No. 7,262,042 and WO09/021867.

(b) trypsin-type or chymotrypsin-type proteases, such as trypsin (e.g.,of porcine or bovine origin), including the Fusarium protease describedin WO 89/06270 and the chymotrypsin proteases derived from Cellumonasdescribed in WO 05/052161 and WO 05/052146.

(c) metalloproteases, including those derived from Bacillusamyloliquefaciens described in WO 07/044993A2.

Preferred proteases include those derived from Bacillus gibsonii orBacillus Lentus.

Suitable commercially available protease enzymes include those soldunder the trade names Alcalase®, Savinase®, Primase®, Durazym®,Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®,Ovozyme®, Neutrase®, Everlase® and Esperase® by Novozymes A/S (Denmark),those sold under the tradename Maxatase®, Maxacal®, Maxapem®,Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®,Excellase® and Purafect OXP® by Genencor International, those sold underthe tradename Opticlean® and Optimase® by Solvay Enzymes, thoseavailable from Henkel/Kemira, namely BLAP (sequence shown in FIG. 29 ofU.S. Pat. No. 5,352,604 with the following mutationsS99D+S101R+S103A+V104I+G159S, hereinafter referred to as BLAP), BLAP R(BLAP with S3T+V4I+V199M+V205I+L217D), BLAP X (BLAP with S3T+V4I+V205I)and BLAP F49 (BLAP with S3T+V4I+A194P+V199M+V205I+L217D)—all fromHenkel/Kemira; and KAP (Bacillus alkalophilus subtilisin with mutationsA230V+S256G+S259N) from Kao.

Suitable alpha-amylases include those of bacterial or fungal origin.Chemically or genetically modified mutants (variants) are included. Apreferred alkaline alpha-amylase is derived from a strain of Bacillus,such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillusstearothermophilus, Bacillus subtilis, or other Bacillus sp., such asBacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, DSM 9375 (U.S. Pat. No.7,153,818) DSM 12368, DSMZ no. 12649, KSM AP1378 (WO 97/00324), KSM K36or KSM K38 (EP 1,022,334). Preferred amylases include:

(a) the variants described in WO 94/02597, WO 94/18314, WO96/23874 andWO 97/43424, especially the variants with substitutions in one or moreof the following positions versus the enzyme listed as SEQ ID No. 2 inWO 96/23874: 15, 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190,197, 202, 208, 209, 243, 264, 304, 305, 391, 408, and 444.

(b) the variants described in U.S. Pat. No. 5,856,164 and WO99/23211, WO96/23873, WO00/60060 and WO 06/002643, especially the variants with oneor more substitutions in the following positions versus the AA560 enzymelisted as SEQ ID No. 12 in WO 06/002643:

26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186,193, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298,299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383,419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484,preferably that also contain the deletions of D183* and G184*.

(c) variants exhibiting at least 90% identity with SEQ ID No. 4 inWO06/002643, the wild-type enzyme from Bacillus SP722, especiallyvariants with deletions in the 183 and 184 positions and variantsdescribed in WO 00/60060, which is incorporated herein by reference.

(d) variants exhibiting at least 95% identity with the wild-type enzymefrom Bacillus sp.707 (SEQ ID NO:7 in U.S. Pat. No. 6,093,562),especially those comprising one or more of the following mutations M202,M208, 5255, R172, and/or M261. Preferably said amylase comprises one ormore of M202L, M202V, M2025, M202T, M202I, M202Q, M202W, S255N and/orR172Q. Particularly preferred are those comprising the M202L or M202Tmutations.

(e) variants described in WO 09/149130, preferably those exhibiting atleast 90% identity with SEQ ID NO: 1 or SEQ ID NO:2 in WO 09/149130, thewild-type enzyme from Geobacillus Stearophermophilus or a truncatedversion thereof.

Suitable commercially available alpha-amylases include DURAMYL®,LIQUEZYME®, TERMAMYL®, TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®,STAINZYME®, STAINZYME PLUS®, FUNGAMYL® and BAN® (Novozymes A/S,Bagsvaerd, Denmark), KEMZYM® AT 9000 Biozym Biotech Trading GmbHWehlistrasse 27b A-1200 Wien Austria, RAPIDASE®, PURASTAR®, ENZYSIZE®,OPTISIZE HT PLUS®, POWERASE® and PURASTAR OXAM® (Genencor InternationalInc., Palo Alto, Calif.) and KAM® (Kao, 14-10 Nihonbashi Kayabacho,1-chome, Chuo-ku Tokyo 103-8210, Japan). In one aspect, suitableamylases include NATALASE®, STAINZYME® and STAINZYME PLUS® and mixturesthereof.

In one aspect, such enzymes may be selected from the group consistingof: lipases, including “first cycle lipases” such as those described inU.S. Pat. No. 6,939,702 B1 and US PA 2009/0217464. In one aspect, thelipase is a first-wash lipase, preferably a variant of the wild-typelipase from Thermomyces lanuginosus comprising one or more of the T231Rand N233R mutations. The wild-type sequence is the 269 amino acids(amino acids 23-291) of the Swissprot accession number Swiss-Prot 059952(derived from Thermomyces lanuginosus (Humicola lanuginosa)). Preferredlipases would include those sold under the tradenames Lipex® andLipolex®.

In one aspect, other preferred enzymes include microbial-derivedendoglucanases exhibiting endo-beta-1,4-glucanase activity (E.C.3.2.1.4), including a bacterial polypeptide endogenous to a member ofthe genus Bacillus which has a sequence of at least 90%, 94%, 97% andeven 99% identity to the amino acid sequence SEQ ID NO:2 in U.S. Pat.No. 7,141,403B2) and mixtures thereof. Suitable endoglucanases are soldunder the tradenames Celluclean® and Whitezyme® (Novozymes A/S,Bagsvaerd, Denmark).

Other preferred enzymes include pectate lyases sold under the tradenamesPectawash®, Pectaway®, Xpect® and mannanases sold under the tradenamesMannaway® (all from Novozymes A/S, Bagsvaerd, Denmark), and Purabrite®(Genencor International Inc., Palo Alto, Calif.).

Enzyme Stabilizing System

The detergent compositions may optionally comprise from about 0.001% toabout 10%, in some examples from about 0.005% to about 8%, and in otherexamples, from about 0.01% to about 6%, by weight of the composition, ofan enzyme stabilizing system. The enzyme stabilizing system can be anystabilizing system which is compatible with the detersive enzyme. Such asystem may be inherently provided by other formulation actives, or beadded separately, e.g., by the formulator or by a manufacturer ofdetergent-ready enzymes. Such stabilizing systems can, for example,comprise calcium ion, boric acid, propylene glycol, short chaincarboxylic acids, boronic acids, chlorine bleach scavengers and mixturesthereof, and are designed to address different stabilization problemsdepending on the type and physical form of the detergent composition. Inthe case of aqueous detergent compositions comprising protease, areversible protease inhibitor, such as a boron compound, includingborate, 4-formyl phenylboronic acid, phenylboronic acid and derivativesthereof, or compounds such as calcium formate, sodium formate and1,2-propane diol may be added to further improve stability.

Builders

The detergent compositions of the present invention may optionallycomprise a builder. Built detergent compositions typically comprise atleast about 1% builder, based on the total weight of the composition.Liquid detergent compositions may comprise up to about 10% builder, andin some examples up to about 8% builder, of the total weight of thecomposition. Granular detergent compositions may comprise up to about30% builder, and in some examples up to about 5% builder, by weight ofthe composition.

Builders selected from aluminosilicates (e.g., zeolite builders, such aszeolite A, zeolite P, and zeolite MAP) and silicates assist incontrolling mineral hardness in wash water, especially calcium and/ormagnesium, or to assist in the removal of particulate soils fromsurfaces. Suitable builders may be selected from the group consisting ofphosphates, such as polyphosphates (e.g., sodium tri-polyphosphate),especially sodium salts thereof; carbonates, bicarbonates,sesquicarbonates, and carbonate minerals other than sodium carbonate orsesquicarbonate; organic mono-, di-, tri-, and tetracarboxylates,especially water-soluble nonsurfactant carboxylates in acid, sodium,potassium or alkanolammonium salt form, as well as oligomeric orwater-soluble low molecular weight polymer carboxylates includingaliphatic and aromatic types; and phytic acid. These may be complementedby borates, e.g., for pH-buffering purposes, or by sulfates, especiallysodium sulfate and any other fillers or carriers which may be importantto the engineering of stable surfactant and/or builder-containingdetergent compositions. Additional suitable builders may be selectedfrom citric acid, lactic acid, fatty acid, polycarboxylate builders, forexample, copolymers of acrylic acid, copolymers of acrylic acid andmaleic acid, and copolymers of acrylic acid and/or maleic acid, andother suitable ethylenic monomers with various types of additionalfunctionalities. Also suitable for use as builders herein aresynthesized crystalline ion exchange materials or hydrates thereofhaving chain structure and a composition represented by the followinggeneral anhydride form: x(M₂O).ySiO₂.zM′O wherein M is Na and/or K, M′is Ca and/or Mg; y/x is 0.5 to 2.0; and z/x is 0.005 to 1.0 as taught inU.S. Pat. No. 5,427,711.

Alternatively, the composition may be substantially free of builder.

Structurant/Thickeners

i. Di-benzylidene Polyol Acetal Derivative

The fluid detergent composition may comprise from about 0.01% to about1% by weight of a dibenzylidene polyol acetal derivative (DBPA), or fromabout 0.05% to about 0.8%, or from about 0.1% to about 0.6%, or evenfrom about 0.3% to about 0.5%. In one aspect, the DBPA derivative maycomprise a dibenzylidene sorbitol acetal derivative (DBS). Said DBSderivative may be selected from the group consisting of:1,3:2,4-dibenzylidene sorbitol; 1,3:2,4-di(p-methylbenzylidene)sorbitol; 1,3:2,4-di(p-chlorobenzylidene) sorbitol;1,3:2,4-di(2,4-dimethyldibenzylidene) sorbitol;1,3:2,4-di(p-ethylbenzylidene) sorbitol; and1,3:2,4-di(3,4-dimethyldibenzylidene) sorbitol or mixtures thereof.

ii. Bacterial Cellulose

The fluid detergent composition may also comprise from about 0.005% toabout 1% by weight of a bacterial cellulose network. The term “bacterialcellulose” encompasses any type of cellulose produced via fermentationof a bacteria of the genus Acetobacter such as CELLULON® by CPKelco U.S.and includes materials referred to popularly as microfibrillatedcellulose, reticulated bacterial cellulose, and the like. In one aspect,said fibres have cross sectional dimensions of 1.6 nm to 3.2 nm by 5.8nm to 133 nm. Additionally, the bacterial cellulose fibres have anaverage microfibre length of at least about 100 nm, or from about 100 toabout 1,500 nm. In one aspect, the bacterial cellulose microfibres havean aspect ratio, meaning the average microfibre length divided by thewidest cross sectional microfibre width, of from about 100:1 to about400:1, or even from about 200:1 to about 300:1.

iii. Coated Bacterial Cellulose

In one aspect, the bacterial cellulose is at least partially coated witha polymeric thickener. In one aspect the at least partially coatedbacterial cellulose comprises from about 0.1% to about 5%, or even fromabout 0.5% to about 3%, by weight of bacterial cellulose; and from about10% to about 90% by weight of the polymeric thickener. Suitablebacterial cellulose may include the bacterial cellulose described aboveand suitable polymeric thickeners include: carboxymethylcellulose,cationic hydroxymethylcellulose, and mixtures thereof.

iv. Cellulose Fibers Non-Bacterial Cellulose Derived

In one aspect, the composition may further comprise from about 0.01 toabout 5% by weight of the composition of a cellulosic fiber. Saidcellulosic fiber may be extracted from vegetables, fruits or wood.Commercially available examples are Avicel® from FMC, Citri-Fi fromFiberstar or Betafib from Cosun.

v. Non-Polymeric Crystalline Hydroxyl-Functional Materials

In one aspect, the composition may further comprise from about 0.01 toabout 1% by weight of the composition of a non-polymeric crystalline,hydroxyl functional structurant. Said non-polymeric crystalline,hydroxyl functional structurants generally may comprise a crystallizableglyceride which can be pre-emulsified to aid dispersion into the finalfluid detergent composition. In one aspect, crystallizable glyceridesmay include hydrogenated castor oil or “HCO” or derivatives thereof,provided that it is capable of crystallizing in the liquid detergentcomposition.

vi. Polymeric Structuring Agents

Fluid detergent compositions of the present invention may comprise fromabout 0.01% to about 5% by weight of a naturally derived and/orsynthetic polymeric structurant. Examples of naturally derived polymericstructurants of use in the present invention include: hydroxyethylcellulose, hydrophobically modified hydroxyethyl cellulose,carboxymethyl cellulose, polysaccharide derivatives and mixturesthereof. Suitable polysaccharide derivatives include: pectine, alginate,arabinogalactan (gum Arabic), carrageenan, gellan gum, xanthan gum, guargum and mixtures thereof. Examples of synthetic polymeric structurantsof use in the present invention include: polycarboxylates,polyacrylates, hydrophobically modified ethoxylated urethanes,hydrophobically modified non-ionic polyols and mixtures thereof. In oneaspect, said polycarboxylate polymer is a polyacrylate, polymethacrylateor mixtures thereof. In another aspect, the polyacrylate is a copolymerof unsaturated mono- or di-carbonic acid and C₁-C₃₀ alkyl ester of the(meth)acrylic acid. Said copolymers are available from Noveon inc underthe tradename Carbopol Aqua 30.

vii. Di-Amido-Gellants

In one aspect, the external structuring system may comprise a di-amidogellant having a molecular weight from about 150 g/mol to about 1,500g/mol, or even from about 500 g/mol to about 900 g/mol. Such di-amidogellants may comprise at least two nitrogen atoms, wherein at least twoof said nitrogen atoms form amido functional substitution groups. In oneaspect, the amido groups are different. In another aspect, the amidofunctional groups are the same. The di-amido gellant has the followingformula:

wherein:R₁ and R₂ is an amino functional end-group, or even amido functionalend-group, in one aspect R₁ and R₂ may comprise a pH-tuneable group,wherein the pH tuneable amido-gellant may have a pKa of from about 1 toabout 30, or even from about 2 to about 10. In one aspect, the pHtuneable group may comprise a pyridine. In one aspect, R₁ and R₂ may bedifferent. In another aspect, may be the same.L is a linking moeity of molecular weight from 14 to 500 g/mol. In oneaspect, L may comprise a carbon chain comprising between 2 and 20 carbonatoms. In another aspect, L may comprise a pH-tuneable group. In oneaspect, the pH tuneable group is a secondary amine.In one aspect, at least one of R₁, R₂ or L may comprise a pH-tuneablegroup.Non-limiting examples of di-amido gellants are:

-   N,N-(2S,2′S)-1,1′-(dodecane-1,12-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)diisonicotinamide

-   dibenzyl    (2S,2′S)-1,1′-(propane-1,3-diylbis(azanediyl))bis(3-methyl-1-oxobutane-2,1-diyl)dicarbamate

-   dibenzyl    (2S,2′S)-1,1′-(dodecane-1,12-diylbis(azanediyl))bis(1-oxo-3-phenylpropane-2,1-diyl)dicarbamate

Polymeric Dispersing Agents

The detergent composition may comprise one or more polymeric dispersingagents. Examples are carboxymethylcellulose, poly(vinyl-pyrrolidone),poly (ethylene glycol), poly(vinyl alcohol),poly(vinylpyridine-N-oxide), poly(vinylimidazole), polycarboxylates suchas polyacrylates, maleic/acrylic acid copolymers and laurylmethacrylate/acrylic acid co-polymers.

The detergent composition may comprise one or more amphiphilic cleaningpolymers such as the compound having the following general structure:bis((C₂H₅O)(C₂H₄O)n)(CH₃)—N⁺—C_(x)H_(2x)—N⁺—(CH₃)-bis((C₂H₅O)(C₂H₄O)n),wherein n=from 20 to 30, and x=from 3 to 8, or sulphated or sulphonatedvariants thereof.

The detergent composition may comprise amphiphilic alkoxylated greasecleaning polymers which have balanced hydrophilic and hydrophobicproperties such that they remove grease particles from fabrics andsurfaces. The amphiphilic alkoxylated grease cleaning polymers maycomprise a core structure and a plurality of alkoxylate groups attachedto that core structure. These may comprise alkoxylatedpolyalkylenimines, for example, having an inner polyethylene oxide blockand an outer polypropylene oxide block. Such compounds may include, butare not limited to, ethoxylated polyethyleneimine, ethoxylatedhexamethylene diamine, and sulfated versions thereof. Polypropoxylatedderivatives may also be included. A wide variety of amines andpolyalklyeneimines can be alkoxylated to various degrees. A usefulexample is 600 g/mol polyethyleneimine core ethoxylated to 20 EO groupsper NH and is available from BASF. The detergent compositions describedherein may comprise from about 0.1% to about 10%, and in some examples,from about 0.1% to about 8%, and in other examples, from about 0.1% toabout 6%, by weight of the detergent composition, of alkoxylatedpolyamines.

Alkoxylated polycarboxylates such as those prepared from polyacrylatesare useful herein to provide additional grease removal performance. Suchmaterials are described in WO 91/08281 and PCT 90/01815. Chemically,these materials comprise polyacrylates having one ethoxy side-chain perevery 7-8 acrylate units. The side-chains are of the formula—(CH₂CH₂O)_(m) (CH₂)—CH₃ wherein m is 2-3 and n is 6-12. The side-chainsare ester-linked to the polyacrylate “backbone” to provide a “comb”polymer type structure. The molecular weight can vary, but is typicallyin the range of about 2000 to about 50,000. The detergent compositionsdescribed herein may comprise from about 0.1% to about 10%, and in someexamples, from about 0.25% to about 5%, and in other examples, fromabout 0.3% to about 2%, by weight of the detergent composition, ofalkoxylated polycarboxylates.

Suitable amphilic graft co-polymer preferable include the amphilic graftco-polymer comprises (i) polyethyelene glycol backbone; and (ii) and atleast one pendant moiety selected from polyvinyl acetate, polyvinylalcohol and mixtures thereof. A preferred amphilic graft co-polymer isSokalan® HP22, supplied from BASF. Suitable polymers include randomgraft copolymers, preferably a polyvinyl acetate grafted polyethyleneoxide copolymer having a polyethylene oxide backbone and multiplepolyvinyl acetate side chains. The molecular weight of the polyethyleneoxide backbone is typically about 6000 and the weight ratio of thepolyethylene oxide to polyvinyl acetate is about 40 to 60 and no morethan 1 grafting point per 50 ethylene oxide units.

Carboxylate polymer—The detergent compositions of the present inventionmay also include one or more carboxylate polymers such as amaleate/acrylate random copolymer or polyacrylate homopolymer. In oneaspect, the carboxylate polymer is a polyacrylate homopolymer having amolecular weight of from 4,000 Da to 9,000 Da, or from 6,000 Da to 9,000Da.

Soil release polymer—The detergent compositions of the present inventionmay also include one or more soil release polymers having a structure asdefined by one of the following structures (I), (II) or (III):—[OCHR¹—CHR²)_(a)—O—OC—Ar—CO—]_(d)  (I)—[OCHR³—CHR⁴)_(b)—O—OC-sAr—CO—]_(e)  (II)—[OCHR⁵—CHR⁶)_(c)—OR⁷]_(f)  (III)

wherein:

a, b and c are from 1 to 200;

d, e and f are from 1 to 50;

Ar is a 1,4-substituted phenylene;

-   -   sAr is 1,3-substituted phenylene substituted in position 5 with        SO₃Me;

Me is Li, K, Mg/2, Ca/2, Al/3, ammonium, mono-, di-, tri-, ortetraalkylammonium wherein the alkyl groups are C₁-C₁₈ alkyl or C₂-C₁₀hydroxyalkyl, or mixtures thereof;

R¹, R², R³, R⁴, R⁵ and R⁶ are independently selected from H or C₁-C₁₈ n-or iso-alkyl; and

R⁷ is a linear or branched C₁-C₁₈ alkyl, or a linear or branched C₂-C₃₀alkenyl, or a cycloalkyl group with 5 to 9 carbon atoms, or a C₈-C₃₀aryl group, or a C₆-C₃₀ arylalkyl group.

Suitable soil release polymers are polyester soil release polymers suchas Repel-o-tex polymers, including Repel-o-tex SF, SF-2 and SRP6supplied by Rhodia. Other suitable soil release polymers include Texcarepolymers, including Texcare SRA100, SRA300, SRN100, SRN170, SRN240,SRN300 and SRN325 supplied by Clariant. Other suitable soil releasepolymers are Marloquest polymers, such as Marloquest SL supplied bySasol.

Cellulosic polymer—The consumer products of the present invention mayalso include one or more cellulosic polymers including those selectedfrom alkyl cellulose, alkyl alkoxyalkyl cellulose, carboxyalkylcellulose, alkyl carboxyalkyl cellulose. In one aspect, the cellulosicpolymers are selected from the group comprising carboxymethyl cellulose,methyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethylcellulose, and mixtures thereof. In one aspect, the carboxymethylcellulose has a degree of carboxymethyl substitution from 0.5 to 0.9 anda molecular weight from 100,000 Da to 300,000 Da.

Examples of polymeric dispersing agents are found in U.S. Pat. No.3,308,067, European Patent Application No. 66915, EP 193,360, and EP193,360.

Amines

Various amines may be used in the detergent compositions describedherein for added removal of grease and particulates from soiledmaterials. The detergent compositions described herein may comprise fromabout 0.1% to about 10%, in some examples, from about 0.1% to about 4%,and in other examples, from about 0.1% to about 2%, by weight of thedetergent composition, of additional amines. Non-limiting examples ofamines include, but are not limited to, polyamines, oligoamines,triamines, diamines, pentamines, tetraamines, polyetheramines, orcombinations thereof. Specific examples of suitable additional aminesinclude tetraethylenepentamine, triethylenetetraamine,diethylenetriamine, polyetheramines, or a mixture thereof.

Bleaching Agents—The detergent compositions of the present invention maycomprise one or more bleaching agents. Suitable bleaching agents otherthan bleaching catalysts include photobleaches, bleach activators,hydrogen peroxide, sources of hydrogen peroxide, pre-formed peracids andmixtures thereof. In general, when a bleaching agent is used, thedetergent compositions of the present invention may comprise from about0.1% to about 50% or even from about 0.1% to about 25% bleaching agentby weight of the detergent composition. Examples of suitable bleachingagents include: photobleaches; preformed peracids; sources of hydrogenperoxide; bleach activators having R—(C═O)-L wherein R is an alkylgroup, optionally branched, having, when the bleach activator ishydrophobic, from 6 to 14 carbon atoms, or from 8 to 12 carbon atomsand, when the bleach activator is hydrophilic, less than 6 carbon atomsor even less than 4 carbon atoms; and L is leaving group. Suitablebleach activators include dodecanoyl oxybenzene sulphonate, decanoyloxybenzene sulphonate, decanoyl oxybenzoic acid or salts thereof,3,5,5-trimethyl hexanoyloxybenzene sulphonate, tetraacetyl ethylenediamine (TAED) and nonanoyloxybenzene sulphonate (NOBS).

Bleach Catalysts—

The detergent compositions of the present invention may also include oneor more bleach catalysts capable of accepting an oxygen atom from aperoxyacid and/or salt thereof, and transferring the oxygen atom to anoxidizeable substrate. Suitable bleach catalysts include, but are notlimited to iminium cations and polyions; iminium zwitterions; modifiedamines; modified amine oxides; N-sulphonyl imines; N-phosphonyl imines;N-acyl imines; thiadiazole dioxides; perfluoroimines; cyclic sugarketones and mixtures thereof.

Brighteners

Optical brighteners or other brightening or whitening agents may beincorporated at levels of from about 0.01% to about 1.2%, by weight ofthe composition, into the detergent compositions described herein.Commercial fluorescent brighteners suitable for the present inventioncan be classified into subgroups, including but not limited to:derivatives of stilbene, pyrazoline, coumarin, benzoxazoles, carboxylicacid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and6-membered-ring heterocycles, and other miscellaneous agents. Examplesof such brighteners are disclosed in “The Production and Application ofFluorescent Brightening Agents”, M. Zahradnik, Published by John Wiley &Sons, New York (1982). Specific nonlimiting examples of opticalbrighteners which are useful in the present compositions are thoseidentified in U.S. Pat. No. 4,790,856, U.S. Pat. No. 3,646,015 U.S. Pat.No. 7,863,236 and its CN equivalent No. 1764714.

In some examples, the fluorescent brightener herein comprises a compoundof formula (1):

wherein: X₁, X₂, X₃, and X₄ are —N(R¹)R², wherein R¹ and R² areindependently selected from a hydrogen, a phenyl, hydroxyethyl, or anunsubstituted or substituted C₁-C₈ alkyl, or —N(R¹)R² form aheterocyclic ring, preferably R¹ and R² are independently selected froma hydrogen or phenyl, or —N(R¹)R² form a unsubstituted or substitutedmorpholine ring; and M is a hydrogen or a cation, preferably M is sodiumor potassium, more preferably M is sodium.

In some examples, the fluorescent brightener is selected from the groupconsisting of disodium4,4′-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate(brightener 15, commercially available under the tradename TinopalAMS-GX by Ciba Geigy Corporation),disodium4,4′-bis{[4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl]-amino}-2,2′-stilbenedisulonate(commercially available under the tradename Tinopal UNPA-GX byCiba-Geigy Corporation), disodium4,4′-bis{[4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl]amino}-2,2′-stilbenedisulfonate(commercially available under the tradename Tinopal 5BM-GX by Ciba-GeigyCorporation). More preferably, the fluorescent brightener is disodium4,4′-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2′-stilbenedisulfonate.The brighteners may be added in particulate form or as a premix with asuitable solvent, for example nonionic surfactant, monoethanolamine,propane diol.

Fabric Hueing Agents

The composition may comprise a fabric hueing agent (sometimes referredto as shading, bluing or whitening agents). Typically the hueing agentprovides a blue or violet shade to fabric. Hueing agents can be usedeither alone or in combination to create a specific shade of hueingand/or to shade different fabric types. This may be provided for exampleby mixing a red and green-blue dye to yield a blue or violet shade.Hueing agents may be selected from any known chemical class of dye,including but not limited to acridine, anthraquinone (includingpolycyclic quinones), azine, azo (e.g., monoazo, disazo, trisazo,tetrakisazo, polyazo), including premetallized azo, benzodifurane andbenzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine,diphenylmethane, formazan, hemicyanine, indigoids, methane,naphthalimides, naphthoquinone, nitro and nitroso, oxazine,phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane,triphenylmethane, xanthenes and mixtures thereof.

Suitable fabric hueing agents include dyes, dye-clay conjugates, andorganic and inorganic pigments. Suitable dyes include small moleculedyes and polymeric dyes. Suitable small molecule dyes include smallmolecule dyes selected from the group consisting of dyes falling intothe Colour Index (C.I.) classifications of Direct, Basic, Reactive orhydrolysed Reactive, Solvent or Disperse dyes for example that areclassified as Blue, Violet, Red, Green or Black, and provide the desiredshade either alone or in combination. In another aspect, suitable smallmolecule dyes include small molecule dyes selected from the groupconsisting of Colour Index (Society of Dyers and Colourists, Bradford,UK) numbers Direct Violet dyes such as 9, 35, 48, 51, 66, and 99, DirectBlue dyes such as 1, 71, 80 and 279, Acid Red dyes such as 17, 73, 52,88 and 150, Acid Violet dyes such as 15, 17, 24, 43, 49 and 50, AcidBlue dyes such as 15, 17, 25, 29, 40, 45, 75, 80, 83, 90 and 113, AcidBlack dyes such as 1, Basic Violet dyes such as 1, 3, 4, 10 and 35,Basic Blue dyes such as 3, 16, 22, 47, 66, 75 and 159, Disperse orSolvent dyes such as those described in EP1794275 or EP1794276, or dyesas disclosed in U.S. Pat. No. 7,208,459 B2, and mixtures thereof. Inanother aspect, suitable small molecule dyes include small molecule dyesselected from the group consisting of C. I. numbers Acid Violet 17,Direct Blue 71, Direct Violet 51, Direct Blue 1, Acid Red 88, Acid Red150, Acid Blue 29, Acid Blue 113 or mixtures thereof.

Suitable polymeric dyes include polymeric dyes selected from the groupconsisting of polymers containing covalently bound (sometimes referredto as conjugated) chromogens, (dye-polymer conjugates), for examplepolymers with chromogens co-polymerized into the backbone of the polymerand mixtures thereof. Polymeric dyes include those described inWO2011/98355, WO2011/47987, US2012/090102, WO2010/145887, WO2006/055787and WO2010/142503.

In another aspect, suitable polymeric dyes include polymeric dyesselected from the group consisting of fabric-substantive colorants soldunder the name of Liquitint® (Milliken, Spartanburg, S.C., USA),dye-polymer conjugates formed from at least one reactive dye and apolymer selected from the group consisting of polymers comprising amoiety selected from the group consisting of a hydroxyl moiety, aprimary amine moiety, a secondary amine moiety, a thiol moiety andmixtures thereof. In still another aspect, suitable polymeric dyesinclude polymeric dyes selected from the group consisting of Liquitint®Violet CT, carboxymethyl cellulose (CMC) covalently bound to a reactiveblue, reactive violet or reactive red dye such as CMC conjugated withC.I. Reactive Blue 19, sold by Megazyme, Wicklow, Ireland under theproduct name AZO-CM-CELLULOSE, product code S-ACMC, alkoxylatedtriphenyl-methane polymeric colourants, alkoxylated thiophene polymericcolourants, and mixtures thereof.

Preferred hueing dyes include the whitening agents found in WO 08/87497A1, WO2011/011799 and WO2012/054835. Preferred hueing agents for use inthe present invention may be the preferred dyes disclosed in thesereferences, including those selected from Examples 1-42 in Table 5 ofWO2011/011799. Other preferred dyes are disclosed in U.S. Pat. No.8,138,222. Other preferred dyes are disclosed in WO2009/069077.

Suitable dye clay conjugates include dye clay conjugates selected fromthe group comprising at least one cationic/basic dye and a smectiteclay, and mixtures thereof. In another aspect, suitable dye clayconjugates include dye clay conjugates selected from the groupconsisting of one cationic/basic dye selected from the group consistingof C.I. Basic Yellow 1 through 108, C.I. Basic Orange 1 through 69, C.I.Basic Red 1 through 118, C.I. Basic Violet 1 through 51, C.I. Basic Blue1 through 164, C.I. Basic Green 1 through 14, C.I. Basic Brown 1 through23, CI Basic Black 1 through 11, and a clay selected from the groupconsisting of Montmorillonite clay, Hectorite clay, Saponite clay andmixtures thereof. In still another aspect, suitable dye clay conjugatesinclude dye clay conjugates selected from the group consisting of:Montmorillonite Basic Blue B7 C.I. 42595 conjugate, MontmorilloniteBasic Blue B9 C.I. 52015 conjugate, Montmorillonite Basic Violet V3 C.I.42555 conjugate, Montmorillonite Basic Green G1 C.I. 42040 conjugate,Montmorillonite Basic Red R1 C.I. 45160 conjugate, Montmorillonite C.I.Basic Black 2 conjugate, Hectorite Basic Blue B7 C.I. 42595 conjugate,Hectorite Basic Blue B9 C.I. 52015 conjugate, Hectorite Basic Violet V3C.I. 42555 conjugate, Hectorite Basic Green G1 C.I. 42040 conjugate,Hectorite Basic Red R1 C.I. 45160 conjugate, Hectorite C.I. Basic Black2 conjugate, Saponite Basic Blue B7 C.I. 42595 conjugate, Saponite BasicBlue B9 C.I. 52015 conjugate, Saponite Basic Violet V3 C.I. 42555conjugate, Saponite Basic Green G1 C.I. 42040 conjugate, Saponite BasicRed R1 C.I. 45160 conjugate, Saponite C.I. Basic Black 2 conjugate andmixtures thereof.

Suitable pigments include pigments selected from the group consisting offlavanthrone, indanthrone, chlorinated indanthrone containing from 1 to4 chlorine atoms, pyranthrone, dichloropyranthrone,monobromodichloropyranthrone, dibromodichloropyranthrone,tetrabromopyranthrone, perylene-3,4,9,10-tetracarboxylic acid diimide,wherein the imide groups may be unsubstituted or substituted byC1-C3-alkyl or a phenyl or heterocyclic radical, and wherein the phenyland heterocyclic radicals may additionally carry substituents which donot confer solubility in water, anthrapyrimidinecarboxylic acid amides,violanthrone, isoviolanthrone, dioxazine pigments, copper phthalocyaninewhich may contain up to 2 chlorine atoms per molecule, polychloro-copperphthalocyanine or polybromochloro-copper phthalocyanine containing up to14 bromine atoms per molecule and mixtures thereof.

In another aspect, suitable pigments include pigments selected from thegroup consisting of Ultramarine Blue (C.I. Pigment Blue 29), UltramarineViolet (C.I. Pigment Violet 15) and mixtures thereof.

The aforementioned fabric hueing agents can be used in combination (anymixture of fabric hueing agents can be used).

Encapsulates

The compositions may comprise an encapsulate. The encapsulate maycomprise a core, a shell having an inner and outer surface, where theshell encapsulates the core.

The encapsulate may comprise a core and a shell, where the corecomprises a material selected from perfumes; brighteners; dyes; insectrepellants; silicones; waxes; flavors; vitamins; fabric softeningagents; skin care agents, e.g., paraffins; enzymes; anti-bacterialagents; bleaches; sensates; or mixtures thereof; and where the shellcomprises a material selected from polyethylenes; polyamides;polyvinylalcohols, optionally containing other co-monomers;polystyrenes; polyisoprenes; polycarbonates; polyesters; polyacrylates;polyolefins; polysaccharides, e.g., alginate and/or chitosan; gelatin;shellac; epoxy resins; vinyl polymers; water insoluble inorganics;silicone; aminoplasts, or mixtures thereof. When the shell comprises anaminoplast, the aminoplast may comprise polyurea, polyurethane, and/orpolyureaurethane. The polyurea may comprise polyoxymethyleneurea and/ormelamine formaldehyde.

The encapsulate may comprise a core, and the core may comprise aperfume. The encapsulate may comprise a shell, and the shell maycomprise melamine formaldehyde and/or cross linked melamineformaldehyde. The encapsulate may comprise a core comprising a perfumeand a shell comprising melamine formaldehyde and/or cross linkedmelamine formaldehyde

Suitable encapsulates may comprise a core material and a shell, wherethe shell at least partially surrounds the core material. At least 75%,or at least 85%, or even at least 90% of the encapsulates may have afracture strength of from about 0.2 MPa to about 10 MPa, from about 0.4MPa to about 5 MPa, from about 0.6 MPa to about 3.5 MPa, or even fromabout 0.7 MPa to about 3 MPa; and a benefit agent leakage of from 0% toabout 30%, from 0% to about 20%, or even from 0% to about 5%.

At least 75%, 85% or even 90% of said encapsulates may have a particlesize of from about 1 microns to about 80 microns, about 5 microns to 60microns, from about 10 microns to about 50 microns, or even from about15 microns to about 40 microns.

At least 75%, 85% or even 90% of said encapsulates may have a particlewall thickness of from about 30 nm to about 250 nm, from about 80 nm toabout 180 nm, or even from about 100 nm to about 160 nm.

The core of the encapsulate comprises a material selected from a perfumeraw material and/or optionally a material selected from vegetable oil,including neat and/or blended vegetable oils including caster oil,coconut oil, cottonseed oil, grape oil, rapeseed, soybean oil, corn oil,palm oil, linseed oil, safflower oil, olive oil, peanut oil, coconutoil, palm kernel oil, castor oil, lemon oil and mixtures thereof; estersof vegetable oils, esters, including dibutyl adipate, dibutyl phthalate,butyl benzyl adipate, benzyl octyl adipate, tricresyl phosphate,trioctyl phosphate and mixtures thereof; straight or branched chainhydrocarbons, including those straight or branched chain hydrocarbonshaving a boiling point of greater than about 80° C.; partiallyhydrogenated terphenyls, dialkyl phthalates, alkyl biphenyls, includingmonoisopropylbiphenyl, alkylated naphthalene, includingdipropylnaphthalene, petroleum spirits, including kerosene, mineral oilor mixtures thereof; aromatic solvents, including benzene, toluene ormixtures thereof; silicone oils; or mixtures thereof.

The wall of the encapsulate may comprise a suitable resin, such as thereaction product of an aldehyde and an amine. Suitable aldehydes includeformaldehyde. Suitable amines include melamine, urea, benzoguanamine,glycoluril, or mixtures thereof. Suitable melamines include methylolmelamine, methylated methylol melamine, imino melamine and mixturesthereof. Suitable ureas include, dimethylol urea, methylated dimethylolurea, urea-resorcinol, or mixtures thereof.

Suitable formaldehyde scavengers may be employed with the encapsulates,for example, in a capsule slurry and/or added to a composition before,during, or after the encapsulates are added to such composition.

Suitable capsules can be purchased from Appleton Papers Inc. ofAppleton, Wis. USA.

In addition, the materials for making the aforementioned encapsulatescan be obtained from Solutia Inc. (St Louis, Mo. U.S.A.), CytecIndustries (West Paterson, N.J. U.S.A.), sigma-Aldrich (St. Louis, Mo.U.S.A.), CP Kelco Corp. of San Diego, Calif., USA; BASF AG ofLudwigshafen, Germany; Rhodia Corp. of Cranbury, N.J., USA; HerculesCorp. of Wilmington, Del., USA; Agrium Inc. of Calgary, Alberta, Canada,ISP of New Jersey U.S.A., Akzo Nobel of Chicago, Ill., USA; StroeverShellac Bremen of Bremen, Germany; Dow Chemical Company of Midland,Mich., USA; Bayer AG of Leverkusen, Germany; Sigma-Aldrich Corp., St.Louis, Mo., USA.

Perfumes

Perfumes and perfumery ingredients may be used in the detergentcompositions described herein. Non-limiting examples of perfume andperfumery ingredients include, but are not limited to, aldehydes,ketones, esters, and the like. Other examples include various naturalextracts and essences which can comprise complex mixtures ofingredients, such as orange oil, lemon oil, rose extract, lavender,musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar, andthe like. Finished perfumes can comprise extremely complex mixtures ofsuch ingredients. Finished perfumes may be included at a concentrationranging from about 0.01% to about 2% by weight of the detergentcomposition.

Dye Transfer Inhibiting Agents

Fabric detergent compositions may also include one or more materialseffective for inhibiting the transfer of dyes from one fabric to anotherduring the cleaning process. Generally, such dye transfer inhibitingagents may include polyvinyl pyrrolidone polymers, polyamine N-oxidepolymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,manganese phthalocyanine, peroxidases, and mixtures thereof. If used,these agents may be used at a concentration of about 0.0001% to about10%, by weight of the composition, in some examples, from about 0.01% toabout 5%, by weight of the composition, and in other examples, fromabout 0.05% to about 2% by weight of the composition.

Chelating Agents

The detergent compositions described herein may also contain one or moremetal ion chelating agents. Suitable molecules include copper, ironand/or manganese chelating agents and mixtures thereof. Such chelatingagents can be selected from the group consisting of phosphonates, aminocarboxylates, amino phosphonates, succinates,polyfunctionally-substituted aromatic chelating agents,2-pyridinol-N-oxide compounds, hydroxamic acids, carboxymethyl inulinsand mixtures thereof. Chelating agents can be present in the acid orsalt form including alkali metal, ammonium, and substituted ammoniumsalts thereof, and mixtures thereof.

Other suitable chelating agents for use herein are the commercialDEQUEST series, and chelants from Monsanto, Akzo-Nobel, DuPont, Dow, theTrilon® series from BASF and Nalco.

The chelant may be present in the detergent compositions disclosedherein at from about 0.005% to about 15% by weight, about 0.01% to about5% by weight, about 0.1% to about 3.0% by weight, or from about 0.2% toabout 0.7% by weight, or from about 0.3% to about 0.6% by weight of thedetergent compositions disclosed herein.

Suds Suppressors

Compounds for reducing or suppressing the formation of suds can beincorporated into the detergent compositions described herein. Sudssuppression can be of particular importance in the so-called “highconcentration cleaning process” as described in U.S. Pat. Nos.4,489,455, 4,489,574, and in front-loading style washing machines.

A wide variety of materials may be used as suds suppressors, and sudssuppressors are well known to those skilled in the art. See, forexample, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). Examples ofsuds supressors include monocarboxylic fatty acid and soluble saltstherein, high molecular weight hydrocarbons such as paraffin, fatty acidesters (e.g., fatty acid triglycerides), fatty acid esters of monovalentalcohols, aliphatic C₁₈-C₄₀ ketones (e.g., stearone), N-alkylated aminotriazines, waxy hydrocarbons preferably having a melting point belowabout 100° C., silicone suds suppressors, and secondary alcohols.

Additional suitable antifoams are those derived from phenylpropylmethylsubstituted polysiloxanes. A suitable antifoam composition comprises:

-   -   a) an organomodified silicone comprising one or more        2-phenylpropylmethyl moieties, preferably 1 to 75 mole percent        2-phenylpropylmethyl moieties, more preferably 5 to 50 mole        percent 2-phenylpropylmethyl moieties, more preferably 5 to 40        mole percent 2-phenylpropylmethyl moieties, most preferably 15        to 25 mole percent 2-phenylpropylmethyl moieties;    -   b) silica;    -   c) a siloxane polymer, said siloxane polymer having a solubility        index of greater than about 0.8, more preferably greater than        0.85, more preferably greater than 0.9, more preferably greater        than 0.95, greater than 0.98, most preferably from about 0.8 to        1.25 and having a viscosity of from about 0.5 cSt to about        10,000 cSt, of from about 0.5 cSt to about 5,000 cSt, of from        about 0.5 cSt to about 1,000 cSt, of from about 2 cSt to about        1,000 cSt, preferably of from about 1 cSt to about 750 cSt, more        preferably of from about 1 cSt to about 500 cSt, more preferably        of from about 1 cSt to about 100 cSt, most preferably of from        about 1 cSt to about 20 cSt; said siloxane polymer having a        viscosity that is about 5%, about 10%, about 20%, about 40%,        about 50%, about 60%, about 75%, about 90%, about 99%, less than        that of said organomodified silicone; and    -   d) a silicone resin;        the antifoam composition having a viscosity, at a shear rate of        20 sec⁻¹ at 25° C., of from about 250 cSt to about 20,000 cSt,        preferably of from about 500 cSt to about 10,000 cSt, more        preferably of from about 1,000 cSt to about 7,000 cSt, most        preferably of from about 1,000 cSt to about 4,000 cSt; a ratio        of organomodified silicone to silica of from about 2:1 to about        500:1, preferably of from about 3:1 to about 100:1, more        preferably of from about 4:1 to about 70:1, most preferably of        from about 5:1 to about 50:1.

The detergent composition may comprise a suds suppressor selected fromorganomodified silicone polymers with aryl or alkylaryl substituentscombined with silicone resin and a primary filler, which is modifiedsilica. The detergent compositions may comprise from about 0.001% toabout 4.0%, by weight of the composition, of such a suds suppressor. Thedetergent composition may comprise a suds suppressor selected from: a)mixtures of from about 80 to about 92% ethylmethyl,methyl(2-phenylpropyl) siloxane; from about 5 to about 14% MQ resin inoctyl stearate; and from about 3 to about 7% modified silica; b)mixtures of from about 78 to about 92% ethylmethyl,methyl(2-phenylpropyl) siloxane; from about 3 to about 10% MQ resin inoctyl stearate; from about 4 to about 12% modified silica; or c)mixtures thereof, where the percentages are by weight of the anti-foam.

The detergent compositions herein may comprise from 0.1% to about 10%,by weight of the composition, of suds suppressor. When utilized as sudssuppressors, monocarboxylic fatty acids, and salts thereof, may bepresent in amounts of up to about 5% by weight of the detergentcomposition, and in some examples, from about 0.5% to about 3% by weightof the detergent composition. Silicone suds suppressors may be utilizedin amounts of up to about 2.0% by weight of the detergent composition,although higher amounts may be used. Monostearyl phosphate sudssuppressors may be utilized in amounts ranging from about 0.1% to about2% by weight of the detergent composition. Hydrocarbon suds suppressorsmay be utilized in amounts ranging from about 0.01% to about 5.0% byweight of the detergent composition, although higher levels can be used.Alcohol suds suppressors may be used at a concentration ranging fromabout 0.2% to about 3% by weight of the detergent composition.

Water-Soluble Film

The compositions of the present invention may also be encapsulatedwithin a water-soluble film. Preferred film materials are preferablypolymeric materials. The film material can, for example, be obtained bycasting, blow-moulding, extrusion or blown extrusion of the polymericmaterial, as known in the art.

Preferred polymers, copolymers or derivatives thereof suitable for useas pouch material are selected from polyvinyl alcohols, polyvinylpyrrolidone, polyalkylene oxides, acrylamide, acrylic acid, cellulose,cellulose ethers, cellulose esters, cellulose amides, polyvinylacetates, polycarboxylic acids and salts, polyaminoacids or peptides,polyamides, polyacrylamide, copolymers of maleic/acrylic acids,polysaccharides including starch and gelatine, natural gums such asxanthum and carragum. More preferred polymers are selected frompolyacrylates and water-soluble acrylate copolymers, methylcellulose,carboxymethylcellulose sodium, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropyl methylcellulose, maltodextrin,polymethacrylates, and most preferably selected from polyvinyl alcohols,polyvinyl alcohol copolymers and hydroxypropyl methyl cellulose (HPMC),and combinations thereof. Preferably, the level of polymer in the pouchmaterial, for example a PVA polymer, is at least 60%. The polymer canhave any weight average molecular weight, preferably from about 1000 to1,000,000, more preferably from about 10,000 to 300,000 yet morepreferably from about 20,000 to 150,000. Mixtures of polymers can alsobe used as the pouch material.

Naturally, different film material and/or films of different thicknessmay be employed in making the compartments of the present invention. Abenefit in selecting different films is that the resulting compartmentsmay exhibit different solubility or release characteristics.

Most preferred film materials are PVA films known under the MonoSoltrade reference M8630, M8900, H8779 and PVA films of correspondingsolubility and deformability characteristics.

The film material herein can also comprise one or more additiveingredients. For example, it can be beneficial to add plasticisers, forexample glycerol, ethylene glycol, diethyleneglycol, propylene glycol,sorbitol and mixtures thereof. Other additives include functionaldetergent additives to be delivered to the wash water, for exampleorganic polymeric dispersants, etc.

Suds Boosters

If high sudsing is desired, suds boosters such as the C₁₀-C₁₆alkanolamides may be incorporated into the detergent compositions at aconcentration ranging from about 1% to about 10% by weight of thedetergent composition. Some examples include the C₁₀-C₁₄ monoethanol anddiethanol amides. If desired, water-soluble magnesium and/or calciumsalts such as MgCl₂, MgSO₄, CaCl₂, CaSO₄, and the like, may be added atlevels of about 0.1% to about 2% by weight of the detergent composition,to provide additional suds and to enhance grease removal performance.

Conditioning Agents

The composition of the present invention may include a high meltingpoint fatty compound. The high melting point fatty compound usefulherein has a melting point of 25° C. or higher, and is selected from thegroup consisting of fatty alcohols, fatty acids, fatty alcoholderivatives, fatty acid derivatives, and mixtures thereof. Suchcompounds of low melting point are not intended to be included in thissection. Non-limiting examples of the high melting point compounds arefound in International Cosmetic Ingredient Dictionary, Fifth Edition,1993, and CTFA Cosmetic Ingredient Handbook, Second Edition, 1992.

The high melting point fatty compound is included in the composition ata level of from about 0.1% to about 40%, preferably from about 1% toabout 30%, more preferably from about 1.5% to about 16% by weight of thecomposition, from about 1.5% to about 8% in view of providing improvedconditioning benefits such as slippery feel during the application towet hair, softness and moisturized feel on dry hair.

The compositions of the present invention may contain a cationicpolymer. Concentrations of the cationic polymer in the compositiontypically range from about 0.05% to about 3%, or from about 0.075% toabout 2.0%, or from about 0.1% to about 1.0%. Suitable cationic polymerswill have cationic charge densities of from about 0.5 meq/gm to about 7meq/gm, at the pH of intended use of the composition, which pH willgenerally range from about pH 3 to about pH 9. Herein, “cationic chargedensity” of a polymer refers to the ratio of the number of positivecharges on the polymer to the molecular weight of the polymer. Theaverage molecular weight of such suitable cationic polymers willgenerally be between about 10,000 and 10 million.

Other suitable cationic polymers for use in the composition includepolysaccharide polymers, cationic guar gum derivatives, quaternarynitrogen-containing cellulose ethers, synthetic polymers, copolymers ofetherified cellulose, guar and starch. When used, the cationic polymersherein are either soluble in the composition or are soluble in a complexcoacervate phase in the composition formed by the cationic polymer andthe anionic, amphoteric and/or zwitterionic surfactant componentdescribed hereinbefore. Complex coacervates of the cationic polymer canalso be formed with other charged materials in the composition.

The composition of the present invention may include a nonionic polymeras a conditioning agent.

Suitable conditioning agents for use in the composition include thoseconditioning agents characterized generally as silicones (e.g., siliconeoils, cationic silicones, silicone gums, high refractive silicones, andsilicone resins), organic conditioning oils (e.g., hydrocarbon oils,polyolefins, and fatty esters) or combinations thereof, or thoseconditioning agents which otherwise form liquid, dispersed particles inthe aqueous surfactant matrix herein. The concentration of the siliconeconditioning agent typically ranges from about 0.01% to about 10%.

The compositions of the present invention may also comprise from about0.05% to about 3% of at least one organic conditioning oil as theconditioning agent, either alone or in combination with otherconditioning agents, such as the silicones (described herein). Suitableconditioning oils include hydrocarbon oils, polyolefins, and fattyesters.

Hygiene and Malodour

The compositions of the present invention may also comprise one or moreof zinc ricinoleate, thymol, quaternary ammonium salts such as Bardac®,polyethylenimines (such as Lupasol® from BASF) and zinc complexesthereof, silver and silver compounds, especially those designed toslowly release Ag⁺ or nano-silver dispersions.

Fillers and Carriers

Fillers and carriers may be used in the detergent compositions describedherein. As used herein, the terms “filler” and “carrier” have the samemeaning and can be used interchangeably.

Liquid detergent compositions and other forms of detergent compositionsthat include a liquid component (such as liquid-containing unit dosedetergent compositions) may contain water and other solvents as fillersor carriers. Suitable solvents also include lipophilic fluids, includingsiloxanes, other silicones, hydrocarbons, glycol ethers, glycerinederivatives such as glycerine ethers, perfluorinated amines,perfluorinated and hydrofluoroether solvents, low-volatilitynonfluorinated organic solvents, diol solvents, and mixtures thereof.

Low molecular weight primary or secondary alcohols exemplified bymethanol, ethanol, propanol, and isopropanol are suitable. Monohydricalcohols may be used in some examples for solubilizing surfactants, andpolyols such as those containing from 2 to about 6 carbon atoms and from2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol,glycerine, and 1,2-propanediol) may also be used. Amine-containingsolvents, such as monoethanolamine, diethanolamine and triethanolamine,may also be used.

The detergent compositions may contain from about 5% to about 90%, andin some examples, from about 10% to about 50%, by weight of thecomposition, of such carriers. For compact or super-compact heavy dutyliquid or other forms of detergent compositions, the use of water may belower than about 40% by weight of the composition, or lower than about20%, or lower than about 5%, or less than about 4% free water, or lessthan about 3% free water, or less than about 2% free water, orsubstantially free of free water (i.e., anhydrous).

For powder or bar detergent compositions, or forms that include a solidor powder component (such as powder-containing unit dose detergentcomposition), suitable fillers may include, but are not limited to,sodium sulfate, sodium chloride, clay, or other inert solid ingredients.Fillers may also include biomass or decolorized biomass. Fillers ingranular, bar, or other solid detergent compositions may comprise lessthan about 80% by weight of the detergent composition, and in someexamples, less than about 50% by weight of the detergent composition.Compact or supercompact powder or solid detergent compositions maycomprise less than about 40% filler by weight of the detergentcomposition, or less than about 20%, or less than about 10%.

For either compacted or supercompacted liquid or powder detergentcompositions, or other forms, the level of liquid or solid filler in theproduct may be reduced, such that either the same amount of activechemistry is delivered to the wash liquor as compared to noncompacteddetergent compositions, or in some examples, the detergent compositionis more efficient such that less active chemistry is delivered to thewash liquor as compared to noncompacted compositions. For example, thewash liquor may be formed by contacting the detergent composition towater in such an amount so that the concentration of detergentcomposition in the wash liquor is from above 0 g/1 to 6 g/l. In someexamples, the concentration may be from about 0.5 g/1 to about 5 g/1, orto about 3.0 g/1, or to about 2.5 g/1, or to about 2.0 g/1, or to about1.5 g/1, or from about 0 g/1 to about 1.0 g/1, or from about 0 g/1 toabout 0.5 g/l. These dosages are not intended to be limiting, and otherdosages may be used that will be apparent to those of ordinary skill inthe art.

Buffer System

The detergent compositions described herein may be formulated such that,during use in aqueous cleaning operations, the wash water will have a pHof between about 7.0 and about 12, and in some examples, between about7.0 and about 11. Techniques for controlling pH at recommended usagelevels include the use of buffers, alkalis, or acids, and are well knownto those skilled in the art. These include, but are not limited to, theuse of sodium carbonate, citric acid or sodium citrate, lactic acid orlactate, monoethanol amine or other amines, boric acid or borates, andother pH-adjusting compounds well known in the art.

The detergent compositions herein may comprise dynamic in-wash pHprofiles. Such detergent compositions may use wax-covered citric acidparticles in conjunction with other pH control agents such that (i)about 3 minutes after contact with water, the pH of the wash liquor isgreater than 10; (ii) about 10 minutes after contact with water, the pHof the wash liquor is less than 9.5; (iii) about 20 minutes aftercontact with water, the pH of the wash liquor is less than 9.0; and (iv)optionally, wherein, the equilibrium pH of the wash liquor is in therange of from about 7.0 to about 8.5.

Catalytic Metal Complexes

The detergent compositions may include catalytic metal complexes. Onetype of metal-containing bleach catalyst is a catalyst system comprisinga transition metal cation of defined bleach catalytic activity, such ascopper, iron, titanium, ruthenium, tungsten, molybdenum, or manganesecations, an auxiliary metal cation having little or no bleach catalyticactivity, such as zinc or aluminum cations, and a sequestrate havingdefined stability constants for the catalytic and auxiliary metalcations, particularly ethylenediaminetetraacetic acid,ethylenediaminetetra(methylenephosphonic acid) and water-soluble saltsthereof.

Other Adjunct Ingredients

A wide variety of other ingredients may be used in the detergentcompositions herein, including other active ingredients, carriers,hydrotropes, processing aids, dyes or pigments, solvents for liquidformulations, and solid or other liquid fillers, erythrosine, colliodalsilica, waxes, probiotics, surfactin, aminocellulosic polymers, ZincRicinoleate, perfume microcapsules, rhamnolipids, sophorolipids,glycopeptides, methyl ester sulfonates, methyl ester ethoxylates,sulfonated estolides, cleavable surfactants, biopolymers, silicones,modified silicones, aminosilicones, deposition aids, locust bean gum,cationic hydroxyethylcellulose polymers, cationic guars, hydrotropes(especially cumenesulfonate salts, toluenesulfonate salts,xylenesulfonate salts, and naphalene salts), antioxidants, BHT, PVAparticle-encapsulated dyes or perfumes, pearlescent agents, effervescentagents, color change systems, silicone polyurethanes, opacifiers, tabletdisintegrants, biomass fillers, fast-dry silicones, glycol distearate,hydroxyethylcellulose polymers, hydrophobically modified cellulosepolymers or hydroxyethylcellulose polymers, starch perfume encapsulates,emulsified oils, bisphenol antioxidants, microfibrous cellulosestructurants, properfumes, styrene/acrylate polymers, triazines, soaps,superoxide dismutase, benzophenone protease inhibitors, functionalizedTiO2, dibutyl phosphate, silica perfume capsules, and other adjunctingredients, silicate salts (e.g., sodium silicate, potassium silicate),choline oxidase, pectate lyase, mica, titanium dioxide coated mica,bismuth oxychloride, and other actives.

The detergent compositions described herein may also contain vitaminsand amino acids such as: water soluble vitamins and their derivatives,water soluble amino acids and their salts and/or derivatives, waterinsoluble amino acids viscosity modifiers, dyes, nonvolatile solvents ordiluents (water soluble and insoluble), pearlescent aids, foam boosters,additional surfactants or nonionic cosurfactants, pediculocides, pHadjusting agents, perfumes, preservatives, chelants, proteins, skinactive agents, sunscreens, UV absorbers, vitamins, niacinamide,caffeine, and minoxidil.

The detergent compositions of the present invention may also containpigment materials such as nitroso, monoazo, disazo, carotenoid,triphenyl methane, triaryl methane, xanthene, quinoline, oxazine, azine,anthraquinone, indigoid, thionindigoid, quinacridone, phthalocianine,botanical, and natural colors, including water soluble components suchas those having C.I. Names. The detergent compositions of the presentinvention may also contain antimicrobial agents.

Processes of Making Detergent Compositions

The detergent compositions of the present invention can be formulatedinto any suitable form and prepared by any process chosen by theformulator.

Methods of Use

The present invention includes methods for cleaning soiled material. Aswill be appreciated by one skilled in the art, the detergentcompositions of the present invention are suited for use in laundrypretreatment applications, laundry cleaning applications, and home careapplications.

Such methods include, but are not limited to, the steps of contactingdetergent compositions in neat form or diluted in wash liquor, with atleast a portion of a soiled material and then optionally rinsing thesoiled material. The soiled material may be subjected to a washing stepprior to the optional rinsing step.

For use in laundry pretreatment applications, the method may includecontacting the detergent compositions described herein with soiledfabric. Following pretreatment, the soiled fabric may be laundered in awashing machine or otherwise rinsed.

Machine laundry methods may comprise treating soiled laundry with anaqueous wash solution in a washing machine having dissolved or dispensedtherein an effective amount of a machine laundry detergent compositionin accord with the invention. An “effective amount” of the detergentcomposition means from about 20 g to about 300 g of product dissolved ordispersed in a wash solution of volume from about 5 L to about 65 L. Thewater temperatures may range from about 5° C. to about 100° C. The waterto soiled material (e.g., fabric) ratio may be from about 1:1 to about30:1. The compositions may be employed at concentrations of from about500 ppm to about 15,000 ppm in solution. In the context of a fabriclaundry composition, usage levels may also vary depending not only onthe type and severity of the soils and stains, but also on the washwater temperature, the volume of wash water, and the type of washingmachine (e.g., top-loading, front-loading, top-loading, vertical-axisJapanese-type automatic washing machine).

The detergent compositions herein may be used for laundering of fabricsat reduced wash temperatures. These methods of laundering fabriccomprise the steps of delivering a laundry detergent composition towater to form a wash liquor and adding a laundering fabric to said washliquor, wherein the wash liquor has a temperature of from about 0° C. toabout 20° C., or from about 0° C. to about 15° C., or from about 0° C.to about 9° C. The fabric may be contacted to the water prior to, orafter, or simultaneous with, contacting the laundry detergentcomposition with water.

Another method includes contacting a nonwoven substrate, which isimpregnated with the detergent composition, with a soiled material. Asused herein, “nonwoven substrate” can comprise any conventionallyfashioned nonwoven sheet or web having suitable basis weight, caliper(thickness), absorbency, and strength characteristics. Non-limitingexamples of suitable commercially available nonwoven substrates includethose marketed under the tradenames SONTARA® by DuPont and POLYWEB® byJames River Corp.

Hand washing/soak methods, and combined handwashing with semi-automaticwashing machines, are also included.

Machine Dishwashing Methods

Methods for machine-dishwashing or hand dishwashing soiled dishes,tableware, silverware, or other kitchenware, are included. One methodfor machine dishwashing comprises treating soiled dishes, tableware,silverware, or other kitchenware with an aqueous liquid having dissolvedor dispensed therein an effective amount of a machine dishwashingcomposition in accord with the invention. By an effective amount of themachine dishwashing composition it is meant from about 8 g to about 60 gof product dissolved or dispersed in a wash solution of volume fromabout 3 L to about 10 L.

One method for hand dishwashing comprises dissolution of the detergentcomposition into a receptacle containing water, followed by contactingsoiled dishes, tableware, silverware, or other kitchenware with thedishwashing liquor, then hand scrubbing, wiping, or rinsing the soileddishes, tableware, silverware, or other kitchenware. Another method forhand dishwashing comprises direct application of the detergentcomposition onto soiled dishes, tableware, silverware, or otherkitchenware, then hand scrubbing, wiping, or rinsing the soiled dishes,tableware, silverware, or other kitchenware. In some examples, aneffective amount of detergent composition for hand dishwashing is fromabout 0.5 ml. to about 20 ml. diluted in water.

Packaging for the Compositions

The detergent compositions described herein can be packaged in anysuitable container including those constructed from paper, cardboard,plastic materials, and any suitable laminates.

Multi-Compartment Pouch Additive

The detergent compositions described herein may also be packaged as amulti-compartment detergent composition.

Analysis Methods and Examples

Assessment of the Biobased Content of Materials

A suitable method to assess materials derived from renewable resourcesis through ASTM D6866, which allows the determination of the biobasedcontent of materials using radiocarbon analysis by accelerator massspectrometry, liquid scintillation counting, and isotope massspectrometry. When nitrogen in the atmosphere is struck by anultraviolet light produced neutron, it loses a proton and forms carbonthat has a molecular weight of 14, which is radioactive. This ¹⁴C isimmediately oxidized into carbon dioxide, which represents a small, butmeasurable fraction of atmospheric carbon. Atmospheric carbon dioxide iscycled by green plants to make organic molecules during the processknown as photosynthesis. The cycle is completed when the green plants orother forms of life metabolize the organic molecules producing carbondioxide, which causes the release of carbon dioxide back to theatmosphere. Virtually all forms of life on Earth depend on this greenplant production of organic molecules to produce the chemical energythat facilitates growth and reproduction. Therefore, the ¹⁴C that existsin the atmosphere becomes part of all life forms and their biologicalproducts. These renewably based organic molecules that biodegrade tocarbon dioxide do not contribute to global warming because no netincrease of carbon is emitted to the atmosphere. In contrast, fossilfuel-based carbon does not have the signature radiocarbon ratio ofatmospheric carbon dioxide.

The application of ASTM D6866 to derive a “biobased content” is built onthe same concepts as radiocarbon dating, but without the use of the ageequations. The analysis is performed by deriving a ratio of the amountof radiocarbon (¹⁴C) in an unknown sample to that of a modem referencestandard. The ratio is reported as a percentage with the units “pMC”(percent modern carbon). If the material being analyzed is a mixture ofpresent day radiocarbon and fossil carbon (containing no radiocarbon),then the pMC value obtained correlates directly to the amount of biomassmaterial present in the sample.

The modern reference standard used in radiocarbon dating is a NIST(National Institute of Standards and Technology) standard with a knownradiocarbon content equivalent approximately to the year AD 1950. Theyear AD 1950 was chosen because it represented a time prior tothermo-nuclear weapons testing, which introduced large amounts of excessradiocarbon into the atmosphere with each explosion (termed “bombcarbon”). The AD 1950 reference represents 100 pMC.

“Bomb carbon” in the atmosphere reached almost twice normal levels in1963 at the peak of testing and prior to the treaty halting the testing.Its distribution within the atmosphere has been approximated since itsappearance, showing values that are greater than 100 pMC for plants andanimals living since AD 1950. The distribution of bomb carbon hasgradually decreased over time, with today's value being near 107.5 pMC.As a result, a fresh biomass material, such as corn, could result in aradiocarbon signature near 107.5 pMC.

Petroleum-based carbon does not have the signature radiocarbon ratio ofatmospheric carbon dioxide. Research has noted that fossil fuels andpetrochemicals have less than about 1 pMC, and typically less than about0.1 pMC, for example, less than about 0.03 pMC. However, compoundsderived entirely from renewable resources have at least about 95 percentmodern carbon (pMC), or at least about 99 pMC, for example, about 100pMC.

Combining fossil carbon with present day carbon into a material willresult in a dilution of the present day pMC content. By presuming that107.5 pMC represents present day biomass materials and 0 pMC representspetroleum derivatives, the measured pMC value for that material willreflect the proportions of the two component types. A material derived100% from present day soybeans would give a radiocarbon signature near107.5 pMC. If that material was diluted with 50% petroleum derivatives,it would give a radiocarbon signature near 54 pMC.

A biobased content result is derived by assigning 100% equal to 107.5pMC and 0% equal to 0 pMC. In this regard, a sample measuring 99 pMCwill give an equivalent biobased content result of 93%.

Assessment of the materials described herein are done in accordance withASTM D6866, particularly with Method B. The mean values quoted in thisreport encompasses an absolute range of 6% (plus and minus 3% on eitherside of the biobased content value) to account for variations inend-component radiocarbon signatures. It is presumed that all materialsare present day or fossil in origin and that the desired result is theamount of biobased component “present” in the material, not the amountof biobased material “used” in the manufacturing process.

GC Sample Preparation

In order to identify the various products of the process, derivatizationis necessary since analysis of oils themselves or fatty acidintermediates is not feasible by direct analysis on this column. Alldata reported herein on the Agilent Technologies Gas Chromatograph 7890Ainstrument are in area %.

Derivatized samples are prepared by drying a 1 ml sample of the reactoreffluent over MgSO₄, filtering, and adding 20 μl of resultant to a vialfollowed by 1.5 ml of 14% BF₃ in MeOH and heating to 65° C. for 30minutes. 1.5 ml of water is then added followed by 2.0 ml of hexane.This is then shaken and the organic layer is allowed to separate. Onceseparated, the top organic layer is dried through a MgSO₄ plug into a GCvial. The resultant sample is analyzed by GC using the following:Agilent Technologies Gas Chromatograph 7890A equipped with asplit/splitless injector and FID, J&W Scientific capillary columnDB-1HT, 30 meter, 0.25 mm id, 0.1 um film thickness cat#1221131, EMDChemicals HPLC grade Chloroform, cat# EM-X1058-1 or equivalent, 2 ml GCautosampler vials with screw tops, or equivalent.

GC Parameters:

Carrier Gas: Helium

Column Head Pressure: 18.5 psi

Flows: Column Flow @ 1.6 ml/min

-   -   Split Vent @ 19.2 ml/min    -   Septum Purge @ 3 ml/min    -   Injection: Agilent Technologies 7693 Series Autosampler, 10 ul        syringe, 1 ul injection    -   Injector Temperature: 275° C.    -   Detector Temperature: 340° C.        Oven Temperature Program: initial 70° C. hold 1 min; rate        10° C./min; final 320° C. hold 5 min.

Another procedure to analyze for impurities in the renewable paraffin is2D GCMS. This system is well known in the analytical literature asproviding a way to separate complex compositions and to identify by massspectroscopy the type of materials separated.

2D GCMS Analysis Procedure:

2D-GC/FID—Relatively Quantitative Comparison

Equipment: Leco Comprehensive 2-dimensional Gas Chromatograph, Agilent7890 GC System (Leco modified) w/split/splitless injector & flameionization detector (FID), Leco Secondary oven, Leco LN2 modulator andcontroller, CTC Combi-PAL Autosampler (or equivalent),

Columns: Supelco Gamma DEX 120 (30m×0.25 mm ID×0.25 um df), Deactivatedtransfer line Restek ‘Siltek’(0.66m×0.25 mm ID), Varian VF-5 ms (2m×0.15mm ID×0.15 um df). In the following configuration:

Film Int. Max Thickness # Type Location Length(m) Diameter(μ) Temp(° C.)(μ) Phase 1 Inlet Front 2 Capillary GC Oven 30.000 250.00 235.0 0.25G-DEX 120 3 Capillary Modulator 0.660 250.00 350.0 0.00 Deactivated FS 4Capillary Secondary Oven 1.770 150.00 360.0 0.15 VF-5ms 5 CapillaryDetector or MS 0.330 150.00 360.0 0.15 VF-5ms Transfer Line

Sample Preparation: Dilute sample 100:1 in dichlormethane (DCM) eg. asfollows: Pipette 10 uL of paraffin or kerosene sample into 2 mL GC vial,Pipette 990 uL DCM into same GC vial, Cap with septa seal and mix(vortex mixer) 20 seconds.

Instrument Parameters: Carrier Gas: Helium @ 1.1 mL/min (constant flowmode), Injection: 1 uL Split 50:1 @200° C., Primary Oven: Initial 35° C.hold 2 min; Ramp 1—1C°/min to 200° C.; Ramp 2—5 C°/min to 220° C.Secondary Oven: +10° C. offset tracking primary oven. Modulator Temp:+25° C. offset tracking primary oven. Modulator Program: Entire run—18.5second modulation period; Hot pulse time—8.75 seconds; Cool time betweenstages 0.5 seconds. Detector: (FID) Temp. 300° C.; Data collection rate:200 Hz; Makeup 25 mL/min Nitrogen (Makeup+column); Hydrogen: 40 mL/min;Air: 450 mL/min.

2D-GC/TOFMS—Qualitative Composition

Equipment: Leco Pegasus 4D—Comprehensive 2-D GC+Time-of-Flight MassSpectrometer; Leco Comprehensive 2-dimensional Gas Chromatograph;Agilent 7890 GC System (Leco modified) w/split/splitless injector &flame ionization detector (FID); Leco Secondary oven; Leco LN2 modulatorand controller; CTC Combi-PAL Autosampler (or equivalent); Columns:Supelco Gamma DEX 120 (30m×0.25 mm ID×0.25 um df), Deactivated transferline ‘Restek Siltek’ (0.4m×0.25 mm ID), Restek rxi-XLB (2.1m×0.18 mmID×0.18 um df). In the following configuration:

Int. Max Film # Type Location Length(m) Diameter(μ) Temp(° C.)Thickness(μ) Phase 1 Inlet Front 2 Capillary GC Oven 30.000 250.00 250.00.25 GDEX 120 3 Capillary Modulator 0.400 250.00 360.0 0.00 DeactivatedFS 4 Capillary Secondary Oven 2.000 180.00 360.0 0.18 rxi-XLB 5Capillary Detector or MS 0.100 180.00 360.0 0.18 rxi-XLB Transfer Line6* Detector TOF

Sample Preparation: Dilute sample 100:1 in dichlormethane (DCM) eg. asfollows: Pipette 10 uL of paraffin or kerosene sample into 2 mL GC vial,Pipette 990 uL DCM into same GC vial, Cap with septa seal and mix(vortex mixer) 20 seconds.

Instrument Parameters: Carrier Gas: Helium @ 1.1 mL/min (constant flowmode), Injection: 1 uL Split 50:1 @200° C., Primary Oven: Initial 35° C.hold 2 min; Ramp 1—1 C°/min to 200° C.; Ramp 2—5 C°/min to 220° C.Secondary Oven: +10° C. offset tracking primary oven. Modulator Temp:+25° C. offset tracking primary oven. Modulator Program: Entire run—18.5second modulation period; Hot pulse time—8.75 seconds; Cool time betweenstages 0.5 seconds. Detector: (TOF-MS): Tranfer line Temperature: 250°C., Data collection rate: 200 spectra/second, Electron Energy: −70V,Mass Range 45—450 m/z, Solvent Delay: 150 seconds, Source Temperature:210° C.

HT-GC/FID—High Temp Fast GC for High Boilers (FFE, & ResidualTriglyceride)

Equipment: Agilent 7890 GC System w/split/splitless injector & flameionization detector (FID); Agilent 7693 Autosampler (or equivalent);Columns: Agilent J&W DB1-HT (5m×0.25 mm ID×0.1 um df—cut from 30m Column#122-1131).

Sample Preparation: Dilute sample 100:1 in dichlormethane (DCM) eg. asfollows: Pipette 10 uL of paraffin or kerosene sample into 2 mL GC vial,Pipette 990 uL DCM into same GC vial, Cap with septa seal and mix(vortex mixer) 20 seconds.

Instrument Parameters: Carrier Gas: Helium @ 1.4 mL/min (constant flowmode); Injection: 1 uL Pulsed Split 25:1 @ 325° C., Pressure Pulse: 10psi until 0.15 min. Oven Program: Initial 40° C. hold 0.5 min; Ramp 1—40C°/min to 380° C. hold 3 min. Detector: (FID) Temp. 380° C., Datacollection rate: 50 Hz, Makeup 25 mL/min Helium, Hydrogen: 40 mL/min,Air: 450 mL/min.

Flow Cat Reactor General Procedure for Examples 1-2:

Catalyst is added to the ½″ FlowCat reaction tube to give a bed lengthof 4 inches. The reaction tube is installed on a HEL E961 FlowCat®. Thesystem is purged 3 times with 300 PSI N2 followed by 3 times 300 PSI H2.The system is pressurized to the operating pressure with H2 and heatedto the operation temperature over 2 hours under operating H₂ flow. Thecatalyst is held under these conditions overnight to activate.Experiments are conducted under conditions outlined in TABLE 1 usingfeed of coconut oil or palm kernel oil, neat or diluted with hexane ascarrier. Non-limiting examples 1 and 2 shown below are result of feed ofcoconut oil.

TABLE 1 Examples 1 and 2. Example 1 2 H₂ Flow ml/min 200 200 Liquid Flowml/min 0.21 0.21 Catalyst Trading Company, ltd. Haldor Topsoe AlbemarleCatalyst ID TK-527 KF-841 (NiMo) (PS—NiMo) Temp ° C. 400 320 Press PSI515 750 GHSV 924 924 LHSV 0.97 0.97 % linear paraffin 93.3 98.0 % ester(see method) 0.0 0.0 % total of branched, cyclic and 5.0 1.6 aromatics %C18+ 1.67 0.43 Ester/Par 0.00 0.00 Even/Odd 3.24 0.53

TABLE 2 Chain Composition of Example 1 vs. Example 2 Example LinearChain 1 2 Length % composition % Composition C8 4.715 2.494 C9 1.2373.142 C10 4.700 2.124 C11 9.362 27.588 C12 33.203 15.645 C13 4.17311.845 C14 13.127 6.105 C15 3.090 8.804 C16 8.867 4.325 C17 3.062 11.080C18 7.800 4.834 other 1.67 0.43 lin par % 93.3 98.0 Even/Odd 3.24 0.53Flow Reactor General Procedure for Examples 4-10:

Catalyst is added to the ½″ 316 stainless steel reaction tube to give abed length of 9 inches. The reaction tube is installed in a flow reactorsystem built from: Brooks Instruments Mass Flow Controller, ModelSLA5850S1CAB1B2A1, S/N 0109120406387001; Brooks Instruments PressureController, Model SLA5820A1CDH1B1A1, S/N 01B20290457; Brooks InstrumentsModel 0254AA1B21A four-channel power supply, readout and set pointcontroller, S/N 011030457589001; J-Kem Scientific 4 channel temperaturecontroller; Applied Test Systems Inc Series 3210 Furnace/Oven, Watts1100, Volts 115, Amps/Zone 9.6, Conn 1-2286-1, with 9 inch heating zone,Max Temp 1650 F, Date 1/10, Serial #09-5152.

The system is purged 3 times with 300 PSI N₂ followed by 3 times 300 PSIH₂. The system is pressurized to the operating pressure with H₂ andheated to the operation temperature over 2 hours under operating H₂flow. The catalyst is held under these conditions overnight to activate.Liquid feed—palm kernel oil, coconut oil, or blends with hexanediluent—is pumped through the system via HPLC pump. Nonlimiting examples3-9 use coconut oil. Experiments are conducted under conditions outlinedin Table 3 with results reported below. The GC analysis method describedabove is used for examples 3-9.

TABLE 3 Examples 3 through 9 EXAMPLE 3 4 5 6 7 8 9 H₂ Flow 500 400 500450 450 450 450 (ml/min) Liquid Flow 0.6 0.4 0.5 0.8 0.3 0.55 0.55(ml/min) Catalyst Trading Haldor Haldor Haldor Haldor Haldor HaldorHaldor Company, ltd. Topsoe Topsoe Topsoe Topsoe Topsoe Topsoe TopsoeCatalyst TK-527 TK-527 TK-527 TK-527 TK-527 TK-527 TK-527 (NiMo) (NiMo)(NiMo) (NiMo) (NiMo) (NiMo) (NiMo) Temp ° C. 406 406 406 385 385 386 367H₂ Pres (PSI) 480 480 480 500 500 500 500 GHSV 1600 1280 1600 1440 14401440 1440 LHSV 1.92 1.28 1.6 2.56 0.96 1.76 1.76 % Linear Paraffin 91.8392.22 92.36 92.57 94.29 95.14 97.32 % Ester 0.34 0.00 0.00 0.54 0.000.00 0.00 % total of branched, 5.56 6.61 6.00 4.43 5.10 3.06 1.66 cyclicand aromatics % C18+ 1.92 1.14 1.63 2.47 0.61 1.79 1.02 Ester/Par 0.000.00 0.00 0.01 0.00 0.00 0.00 Even/Odd 5.64 4.86 5.63 3.47 4.37 3.762.42

The chain composition can be modified depending on the choice ofcatalyst, such as Ni/Mo or Ni/Mo sulfurized, leading to various ratiosof even and odd chains, from increased even to odd ratios to decreasedeven to odd ratios. This can be beneficial depending on the selection ofchain cuts desired by the end user of the surfactant, e.g., therenewable linear alkyl benzene or the renewable detergent alcohol of theinvention.

The same procedure as in examples 3-9 is followed for examples 10-11.Examples 10-11 use coconut oil as feed. Experiments are conducted underconditions outlined in Table 4 for this catalyst with results reportedbelow. The GC analysis method described above is used for examples10-11.

TABLE 4 Pd/Alumina and Pd/Carbon data for examples 10-11. EXAMPLE 10 11Supplier Jm/Alfa Aesar Aldrich Catalyst 5% Pd/Al 5% Pd/C H2 Flow(ml/min) 50 100    Liquid Flow (ml/min) 0.6 0.4  Temp ° C. 403 330    H₂Pres (PSI) 300 300    GHSV 240 240*    LHSV 1.92 192*    % LinearParaffin 89.40 98.52  % Ester 6.652 0.36 % total of branched, cyclic,aromatics 7.572 1.11 % C18+ 3.029 0.27 Ester/Par 0.142 0.00 Even/Odd0.003 0.01 *not measured but predicted to be similar to example 10

As shown in Table 5, by using 2D GCMS analysis, more detail onimpurities may be obtained than via standard GC analysis on Examples 1,2, and 9. Purity of the renewable linear paraffin is shown to be greaterthan 90%.

TABLE 5 analysis of samples via 2D GCMS: 2D-GC/FID Results Example 1 2 9Paraffin 99.4 94.4 99.8 linear 98.9 94.1 98.9 branched 0.5 0.3 0.9Olefin/Cyclic 0.5 5.4 0.2 Alcohol 0 0.1 0 Aldehyde 0 0 0 Ester 0.1 0.1 0

Example 12

Renewable linear alkyl benzene and renewable detergent alcoholproduction using the renewable linear paraffin product of example 3. Therenewable linear paraffin product of Example 3 is provided to a gasremoval unit (FIG. 2, 9) to remove volatile gases and short chainhydrocarbons and then is provided to a standard petroleum refiningfractionation unit (FIG. 2, 10) to provide three cuts ofparaffins—C10-13 (cut 1), C14-16 (cut 2), and C17-C18 (cut 3). Cut 1 issent to a dehydrogenation unit (FIG. 2, 13) and then to an alkylationunit (FIG. 2, 14), where it is alkylated with benzene to provide arenewable (partially, petrol-based benzene) alkyl benzene. Procedures toremove benzene and heavy distillate from the renewable alkyl benzeneproduct are known to one skilled in the art. Cut 2 is sent to anotherdehydrogenation unit (FIG. 2, 15) followed by the step of olefinabsorptive separation to provide a high purity renewable linear olefinmixture, which is further subjected to a selective hydroformylationcatalyst in a hydroformylation unit (FIG. 2, 16) to provide a renewable,mostly linear, detergent alcohol. Optionally, cut 3 is sent to asulfoxidation unit (FIG. 2 a, 17) to provide a renewable paraffinsulfonate surfactant.

Example 13

Renewable linear alkyl benzene and renewable detergent alcoholproduction using the renewable linear paraffin product of example 9. Therenewable linear paraffin product of Example 9 is provided to gasremoval unit (FIG. 2, 9) to remove the volatile gases and short chainhydrocarbons and then is provided to a standard petroleum refiningfractionation unit (FIG. 2, 10) to provide three cuts ofparaffins—C10-13 (cut 1), C14-16 (cut 2), and C17-C18 (cut 3). Cut 1 issent to a dehydrogenation unit (FIG. 2, 13) and then to an alkylationunit (FIG. 2, 14), where it is alkylated with benzene to provide arenewable (partially, petrol-based benzene) alkyl benzene. Procedures toremove benzene and heavy distillate from the renewable alkyl benzeneproduct are known to one skilled in the art. Cut 2 is sent to anotherdehydrogenation unit (FIG. 2, 15) followed by the step of olefinabsorptive separation to provide a high purity renewable linear olefinmixture, which is further subjected to a non-selective hydroformylationcatalyst in a hydroformylation unit (FIG. 2, 16) to provide a renewabledetergent alcohol mixture with greater than 25% 2-alkyl alkanol.Optionally, cut 3 is sent to a sulfoxidation unit (FIG. 2 a, 17) toprovide a renewable paraffin sulfonate surfactant.

Example 14

Renewable linear alkyl benzene sulfonate. The renewable linear alkylbenzene product of example 13 is sulfonated in a standard falling filmsulfonator unit and subsequently neutralized providing a renewablelinear alkyl benzene sulfonate surfactant.

Example 15

Renewable detergent alcohol sulfate containing greater than 25% 2-alkylalkanol sulfate. The renewable detergent alcohol of example 13 issulfated under standard conditions and neutralized.

Example 16

Blends of renewable alkyl benzene sulfonate and renewable detergentalcohol sulfate. The renewable linear alkyl benzene sulfonate of example14 is blended with the renewable detergent alcohol sulfate of example 15in weight ratios from about 1:99 to about 99:1 to provide a renewablesurfactant mixture.

Example 17

Renewable ethoxylated sulfate. The renewable alcohol of example 12 isethoxylated using standard procedures to an ethoxylate average of about1.8 and subsequently sulfated in a standard falling film sulfonationprocess to provide a renewable ethoxylate sulfate that is substantiallylinear.

Example 18

Blends of example 14, 15 and 17. The renewable surfactants of example14,15 and 17 are blended in various ratios to provide three-componentblends of the renewable surfactant mixtures.

Example 19

Blends of example 15 and standard natural alcohol ethoxylated sulfates.Natural alcohol ethoxylated sulfates with an average degree ofethoxylation of about 3 are blended with example 15 to provide arenewable surfactant mixture.

Example 20

Liquid Liquid Liquid Liquid Detergent Detergent Detergent Detergent A(wt %) B (wt %) C (wt %) D (wt %) AES C₁₂₋₁₅ alkyl ethoxy (1.8) sulfate1-12 0    1-12  1-12 1-12 Alkyl benzene sulfonate ² 1-5  0   1-5 1-51-10 Sodium formate 2.66 2.66 2.66 2.66 0.11 Calcium formate — — — — 0.097 Sodium hydroxide 0.21 0.21 0.21 0.21 0.68 Monoethanolamine (MEA)1.65 1.65 1.65 1.65 2.80 Diethylene glycol (DEG) 4.10 4.10 4.10 4.101.23 Propylene glycol — — — — 8.39 AE9³ 0.40 0.40 0.40 0.40 — C16AE73.15 3.15 3.15 3.15 — NI 24-9¹³ — — — — 0.97 Renewable Surfactant¹¹ 5-2015-30 1-5 10-20 1-5  Chelant⁴ 0.18 0.18 0.18 0.18 0.29 Citric Acid 1.701.70 1.70 1.70 2.83 C₁₂₋₁₈ Fatty Acid 1.47 1.47 1.47 1.47 1.09 Borax1.19 1.19 1.19 1.19 2.00 Ethanol 1.44 1.44 1.44 1.44 1.47 EthoxylatedPolyethyleneimine ¹ 1.35 1.35 1.35 1.35 1.85 Amphiphilic alkoxylatedgrease — — — —  0.940 cleaning polymer¹² A compound having the following0.40 0.40 0.40 0.40 1.40 general structure: bis((C₂H₅O)(C₂H₄O)n)(CH₃)—N⁺—C_(x)H_(2x)—N⁺—(CH₃)— bis((C₂H₅O)(C₂H₄O)n), wherein n = from 20 to30, and x = from 3 to 8, or sulphated or sulphonated variants thereof1,2-Propanediol 2.40 2.40 2.40 2.40 — Protease (54.5 mg active/g)⁹ 0.890.89 0.89 0.89 0.95 Mannanase: Mannaway ® (25.6 mg 0.04 0.04 0.04 0.04 —active/g)⁵ Xyloglucanase: Whitezyme ® (20 — — — — 0.04 mg active/g)¹⁴Cellulase: Carezyme ™ (11.63 — — — — 0.10 mg active/g)¹⁴ Amylase:Natalase ® (29 mg 0.14 0.14 0.14 0.14 0.34 active/g)⁵ FluorescentWhitening Agents¹⁰ 0.10 0.10 0.10 0.10 0.15 Water, perfume, dyes & otherBalance Balance components ¹ Polyethyleneimine (MW = 600) with 20ethoxylate groups per —NH. ² Linear alkylbenzenesulfonate having anaverage aliphatic carbon chain length C₁₁-C₁₂ supplied by Stepan,Northfield, Illinois, USA ³AE9 is C₁₂₋₁₃ alcohol ethoxylate, with anaverage degree of ethoxylation of 9, supplied by Huntsman, Salt LakeCity, Utah, USA ⁴Suitable chelants are, for example,diethylenetetraamine pentaacetic acid (DTPA) supplied by Dow Chemical,Midland, Michigan, USA or Hydroxyethane di phosphonate (HEDP) suppliedby Solutia, St Louis, Missouri, USA Bagsvaerd, Denmark ⁵Natalase ®,Mannaway ® are all products of Novozymes, Bagsvaerd, Denmark. 6.Proteases may be supplied by Genencor International, Palo Alto,California, USA (e.g. Purafect Prime ®) or by Novozymes, Bagsvaerd,Denmark (e.g. Liquanase ®, Coronase ®). ¹⁰Suitable Fluorescent WhiteningAgents are for example, Tinopal ® AMS, Tinopal ® CBS-X, Sulphonated zincphthalocyanine Ciba Specialty Chemicals, Basel, Switzerland ¹¹Renewablesurfactant of Example 14, 15, 16, 17, 18, or 19. ¹²Amphiphilicalkoxylated grease cleaning polymer is a polyethyleneimine (MW = 600)with 24 ethoxylate groups per —NH and 16 propoxylate groups per —NH.¹³Huntsman, Salt Lake City, Utah, USA. ¹⁴Novozymes A/S, Bagsvaerd,Denmark.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm”

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A method for producing an alkylbenzene and adetergent alcohol from a natural oil and petrol-based kerosenecomprising: a) providing a first feed stream comprising natural oil; b)deoxygenating said first feed stream to form a stream comprisingbio-paraffins; c) removing volatile components and gases from saidstream comprising bio-paraffins to form a purified bio-paraffin stream;d) fractionating said purified bio-paraffin stream into three fractions,wherein a first fraction comprises a lower boiling range, a secondfraction comprises a middle boiling range, and a third fractioncomprises a high boiling range; e) providing a second stream comprisingpetrol-based kerosene; f) hydrotreating said second stream; g) sievingsaid hydrotreated second stream to form a stream comprisingkerosene-based paraffin; h) combining said first fraction of purifiedbio-paraffin with said kerosene-based paraffin to form a combination,wherein greater than 50 wt % of said combination of said first fractionof purified bio-paraffin and said kerosene-based paraffin is derivedfrom natural oil; i) dehydrogenating said combination of said firstfraction of purified bio-paraffin and said kerosene-based paraffin toform a stream comprising olefins; j) alkylating said stream comprisingolefins with a third feed stream comprising benzene to form a streamcomprising alkylbenzenes; k) dehydrogenating said second fraction ofpurified bio-paraffin to form a stream comprising olefins and paraffins;l) separating said olefins from said paraffins in said stream comprisingolefins and paraffins to form an olefin stream; m) hydroformylating saidolefin stream to form a stream comprising detergent alcohols.
 2. Themethod of claim 1, wherein said third fraction of purified bio-paraffinis sulfoxidized to form a stream comprising paraffin sulfonate.
 3. Themethod of claim 1, wherein said purified paraffin stream has greaterthan about 90% purity, wherein said purified paraffin stream comprisesless than about 5% branched paraffins, less than about 3% olefins andcyclic compounds, and less than about 2% alcohols, esters, aldehydes,and fatty acids.
 4. The method of claim 1, wherein said purifiedbio-paraffin stream comprises paraffins ranging in chain length from C10to C18.
 5. The method of claim 1, wherein said third feed streamcomprises renewable benzene.
 6. The method of claim 1, wherein saidnatural oil is selected from the group consisting of coconut oil, palmkernel oil, palm oil, and mixtures thereof.
 7. The method of claim 1,wherein said alkylbenzenes are sulfonated.
 8. The method of claim 1,wherein said detergent alcohols are sulfated.